CN106458797B - The manufacturing method of 1,1,2- tribromoethane - Google Patents
The manufacturing method of 1,1,2- tribromoethane Download PDFInfo
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- CN106458797B CN106458797B CN201580022949.4A CN201580022949A CN106458797B CN 106458797 B CN106458797 B CN 106458797B CN 201580022949 A CN201580022949 A CN 201580022949A CN 106458797 B CN106458797 B CN 106458797B
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Abstract
The purpose of the present invention is to provide a kind of manufacturing methods of the 1,1,2- tribromoethane of low cost and high income.The present invention is the manufacturing method of 1,1,2- tribromoethane comprising by 1,1,2- tri- halogen ethane bromination shown in formula (1), obtains the process A of 1,1,2- tribromoethane.[in formula, X1、X2And X3Indicate chlorine atom or bromine atom, wherein X1、X2And X3Middle at least one is chlorine atom.]
Description
Technical field
The present invention relates to the manufacturing methods of 1,1,2- tribromoethane.
Background technique
1,1- dibromoethylene is the conjunction as the synthetic intermediate, optical fiber outsourcing material of medical (such as antibiotic)
At intermediate, the synthetic intermediate of coating material, the synthetic intermediate of semiconductor corrosion resistant material and functional high-polymer list
The useful compound such as the synthetic intermediate of body.
It is known in the art that 1,1- dibromoethylene can react to obtain by the dehydrobromination of 1,1,2- tribromoethane
(patent document 1).
Here, 1 of the raw material as the manufacturing method disclosed in patent document 1, can lead to known to 1,2- tribromoethane
The bromine addition reaction for crossing ethylene bromide obtains (non-patent literature 1).
In addition, being individually disclosed in patent document 2~4 using hydrogen bromide or aluminium and bromine by alkyl chloride manufacture alkyl bromide
Method.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 50-52006 bulletin
Patent document 2: No. 1891415 specifications of U.S. Patent No.
Patent document 3: No. 2120675 specifications of U.S. Patent No.
Patent document 4: No. 2057964 specifications of U.S. Patent No.
Non-patent literature
Non-patent literature 1:Synthesis, 1999, p.2131-2137
Summary of the invention
Problems to be solved by the invention
In manufacturing method described in above-mentioned non-patent literature 1, as raw material ethylene bromide must by the bromination of ethylene,
Then it is manufactured by dehydrobromination reaction, therefore, process number and waste are more, when industrially utilizing, from manufacturing cost etc.
From the viewpoint of be unfavorable.
In addition, manufacturing method as described in patent document 2~4, when using alkyl chloride as raw material, according to the present invention
Inventor research, the yield and purity of the alkyl bromide as target be low.
Therefore, the purpose of the present invention is to provide a kind of manufacturers of 1,1,2- tribromoethane of low cost and high income
Method.
In addition, it is another object of the present invention to provide the manufactures of a kind of low cost and 1, the 1- dibromoethylene of high income
Method.
The method used for solving the problem
The present inventor has made intensive studies, as a result, it has been found that, by by 1,1,2- tri- halogen ethane shown in formula (1)
Chlorine atom be converted into bromine atom, low cost and 1,1,2- tribromoethane can be manufactured in high yield, it is further studying as a result,
Complete the present invention.
In formula,
X1、X2And X3Indicate chlorine atom or bromine atom.
Wherein, X1、X2And X3Middle at least one is chlorine atom.?
The present invention includes such as under type.
Item 1.
The manufacturing method of one kind 1,1,2- tribromoethane comprising by 1,1,2- tri- halogen ethane bromine shown in following formula (1)
Change, obtains the process A of 1,1,2- tribromoethane.
In formula,
X1、X2And X3Indicate chlorine atom or bromine atom.
Wherein, X1、X2And X3Middle at least one is chlorine atom.?
Item 2.
Manufacturing method as described in item 1, wherein 1,1,2- tri- halogen ethane shown in above-mentioned formula (1) is the bromo- 1- chlorine of 1,2- bis-
Ethane or 1,1,2- trichloroethanes.
Item 3.
Manufacturing method as described in item 1 or 2, wherein in process A, make 1,1,2- tri- halogen ethane shown in above-mentioned formula (1) with
Aluminium and bromine reaction obtain 1,1,2- tribromoethane.
Item 4.
Manufacturing method as described in any one of item 1, wherein in process A, make 1,1,2- tri- shown in above-mentioned formula (1)
Halogen ethane obtains 1,1,2- tribromoethane with the halogenation reactive aluminum of 1 or more bromine atom.
Item 5.
Manufacturing method as described in item 4, wherein the above-mentioned aluminum halide with 1 or more bromine atom is aluminium bromide.
Item 6.
Manufacturing method as described in any one of item 1~5, wherein model of the reaction temperature of process A at -78 DEG C~20 DEG C
In enclosing.
Item 7.
Manufacturing method as described in any one of item 1~6, wherein process A has the halogenated alkyl as reaction dissolvent
Implement under conditions of compound.
Item 8.
The manufacturing method of one kind 1,1- dibromoethylene comprising manufacture described in any one of item 1~7 will be passed through using alkali
1,1, the 2- tribromoethane dehydrobromination that method obtains, obtains the process B of 1,1- dibromoethylene.
Item 9.
Manufacturing method as described in item 8, wherein process B has water-miscible organic solvent or water as reaction dissolvent
Implement under conditions of the mixed solvent of solubleness organic solvent and water.
Item 10.
Manufacturing method as described in item 8, wherein process B there are water and be not present water-miscible organic solvent under conditions of
Implemented using phase transfer catalyst.
Item 11.
Manufacturing method as described in any one of item 8~10, wherein process B is there are a kind or more of amine compounds and choosings
Implement under conditions of the compound of one or more of following (1)~(5),
(1) with hydroxyl compound,
(2) with thioether bond compound,
(3) compound with thiophenol or mercaptan sulphur atom,
(4) hydrosulfide,
(5) nitrous compound.
The effect of invention
In accordance with the invention it is possible to provide the manufacturing method of low cost and 1,1,2- tribromoethane of high income.
In addition, in accordance with the invention it is possible to providing the manufacturing method of low cost and 1, the 1- dibromoethylene of high income.
Specific embodiment
The manufacturing method of 1,1,2- tribromoethane
The manufacturing method of 1,1,2- tribromoethane of the invention includes by tri- halogen ethane bromine of 1,1,2- shown in above-mentioned formula (1)
Change and obtains the process A of 1,1,2- tribromoethane.
Tri- halogen ethane of 1,1,2- shown in above-mentioned formula (1) used in process A by well known method or can be based on
Its method manufacture.Also, 1,1,2- tri- halogen ethane can be obtained by commercial channel.
It is bromo- as 1,1,2- tri- halogen ethane shown in used in process A, above-mentioned formula (1), such as preferably 1,2- bis-
1- chloroethanes or 1,1,2- trichloroethanes.As 1,1,2- tri- halogen ethane shown in above-mentioned formula (1), it is bromo- that 1,2- bis- can be used
The mixture of 1- chloroethanes and 1,1,2- trichloroethanes.
Wherein, from the viewpoint of the generation that height inhibits by-product, the bromo- 1- chloroethanes of particularly preferred 1,2- bis-.
In 1,1,2- tri- halogen ethane shown in above-mentioned formula (1), 1,2- bis- bromo- 1- chloroethanes is specifically for example fitted through
Including manufacturing the method for the process of vinyl chloride addition bromine.According to this method, it is able to use and is easy to start with and cheap chloroethene
Alkene manufactures the bromo- 1- chloroethanes of 1,2- bis-, therefore is advantageous.Manufacturing method about the bromo- 1- chloroethanes of 1,2- bis- is rear
Face is described in detail.
In a preferred mode of the invention, reaction (1,1, the 2- tri- halogen ethane shown in i.e. above-mentioned formula (1) of process A
Bromination) preferably implemented by making tri- halogen ethane of 1,1,2- shown in above-mentioned formula (1) with aluminium and bromine reaction.That is, in which,
In process A, 1,1,2- tri- halogen ethane shown in above-mentioned formula (1) and aluminium and bromine reaction is made to obtain 1,1,2- tribromoethane.
The form of aluminium is not particularly limited, for example, can be in the form of powder, granular or foil-like etc. are common in process A
It uses.
Relative to 1,1,2- tri- halogen ethane shown in above-mentioned formula (1), the amount of aluminium is preferably in 0.1 equivalent~5 equivalents range
It is interior, more preferably in the range of 0.1 equivalent~3 equivalent, further preferably in the range of 0.2 equivalent~2 equivalent.
Bromine can be together with aftermentioned solvent (for example, in the form of the bromine being dissolved in aftermentioned solvent) to the anti-of process A
It answers in system and adds.
Relative to 1,1,2- tri- halogen ethane shown in above-mentioned formula (1), the amount of bromine is preferably in 0.1 equivalent~5 equivalents range
It is interior, more preferably in the range of 0.1 equivalent~3 equivalent, further preferably in the range of 0.1 equivalent~2 equivalent.
In addition, the reaction of process A is (1,1,2- shown in i.e. above-mentioned formula (1) in an other preferred mode of the invention
The bromination of three halogen ethane) preferably by making tri- halogen ethane of 1,1,2- shown in above-mentioned formula (1) and the halogen with 1 or more bromine atom
Change reactive aluminum to implement.That is, in which, in process A, make 1,1,2- tri- halogen ethane shown in above-mentioned formula (1) with have 1 with
The halogenation reactive aluminum of upper bromine atom obtains 1,1,2- tribromoethane.As the aluminum halide with 1 or more bromine atom, for example,
AlBrCl can be enumerated2、AlBr2Cl、AlBrF2、AlBr2F, AlBrClF and AlBr3(aluminium bromide).Aluminum halide can be used alone
1 kind, or two or more use can also be combined.As the aluminum halide with 1 or more bromine atom, preferably AlBrCl2、
AlBr2Cl or AlBr3, more preferably AlBr3。
The amount of aluminum halide with 1 or more bromine atom is different according to the type of aluminum halide, relative to above-mentioned formula
(1) 1,1,2- tri- halogen ethane shown in, preferably in the range of 0.1 equivalent~5 equivalent, more preferably in 0.1 equivalent~3 equivalents
In range, further preferably in the range of 0.2 equivalent~2 equivalent.
The suitable reaction temperature of process A is according to the raw material compound of process A (that is, 1,1,2- tri- shown in above-mentioned formula (1)
Halogen ethane) and it is different, and in one embodiment of the present invention, the upper limit of the reaction temperature of process A is preferably 50 DEG C, more preferably
20℃；The lower limit of the reaction temperature of process A be preferably -78 DEG C, more preferably -60 DEG C, further preferably -50 DEG C, more into
One step is preferably -40 DEG C；The reaction temperature of process A is preferably in the range of -78 DEG C~50 DEG C, more preferably -60 DEG C~20
In the range of DEG C, further preferably in the range of -50 DEG C~20 DEG C or -50 DEG C~-20 DEG C, still more preferably -
In the range of 40 DEG C~20 DEG C or -40 DEG C~-20 DEG C.
For the suitable reaction temperature of process A in an other mode, the upper limit of the reaction temperature of process A is preferably 20
DEG C, more preferably 0 DEG C；Preferably -78 DEG C of the lower limit of the reaction temperature of process A, more preferably -60 DEG C, further preferably
It is -50 DEG C, is still more preferably -40 DEG C；The reaction temperature of process A is more excellent preferably in the range of -78 DEG C~20 DEG C
It is selected in the range of -50 DEG C~0 DEG C, further preferably in the range of -50 DEG C~-10 DEG C, still more preferably -40
DEG C~-10 DEG C in the range of.
In the case that the raw material compound of process A is the bromo- 1- chloroethanes of 1,2- bis-, the upper limit of reaction temperature is preferably 20
DEG C, more preferably 10 DEG C, further preferably 0 DEG C；Preferably -78 DEG C of the lower limit of reaction temperature, more preferably -60 DEG C, into
One step is preferably -40 DEG C；The reaction temperature of process A is preferably in the range of -78 DEG C~20 DEG C, more preferably -60 DEG C~10
In the range of DEG C, further preferably in the range of -40 DEG C~0 DEG C.
In the case that the raw material compound of process A is 1,1,2- trichloroethanes, the upper limit of reaction temperature is preferably 20 DEG C, more
Preferably 10 DEG C, further preferably 5 DEG C；The lower limit of reaction temperature is preferably -78 DEG C, more preferably -50 DEG C, further excellent
It is selected as -30 DEG C；The reaction temperature of process A is preferably in the range of -78 DEG C~20 DEG C, more preferably in -50 DEG C~10 DEG C of model
In enclosing, further preferably in the range of -30 DEG C~5 DEG C.
When the reaction temperature of process A is excessively high, there are the trend that the yield of 1,1,2- tribromoethane reduces.
But the reaction temperature of process A it is low when, so that reaction temperature is formed such low temperature itself and be difficult, in cost
Aspect it is unfavorable.
Therefore, for the reaction temperature of process A when the yield of 1,1,2- tribromoethane is abundant, usually the higher the better.
The reaction time of process A is usually in the range of 0.5~10 hour.
Process A can be there are reaction dissolvent or there is no implement under conditions of reaction dissolvent.
From the viewpoint of the reliability carried out from reaction is high, process A is preferably implemented under conditions of there are reaction dissolvent.
When process A is implemented under conditions of there are reaction dissolvent, which is preferably that halo-alkyl solvents are (halogenated
Alkyl compound).
As the halo-alkyl solvents, for example, chlorine series solvent, bromine series solvent and fluorine series solvent can be enumerated.Chlorine series solvent
Refer to that the solvent containing chlorine atom, bromine series solvent refer to that the solvent containing bromine atom, fluorine series solvent refer to containing the molten of fluorine atom
Agent.It avoids repeatedly being illustrated here hereinafter, illustrating chlorine series solvent, bromine series solvent and fluorine series solvent.That is, for example,
CH3CClF2It is fluorine series solvent, while is also chlorine series solvent.
Chlorine series solvent can be the halo-alkyl solvents only as halogen atom with chlorine atom.
Bromine series solvent can be the halo-alkyl solvents only as halogen atom with bromine atom.
Fluorine series solvent can be the halo-alkyl solvents only as halogen atom with fluorine atom.
As chlorine series solvent, for example, methylene chloride, chloroform, carbon tetrachloride, chloroethanes, 1,1-, bis- chloroethene can be enumerated
Alkane, 1,2- dichloroethanes, n-propyl chloride, 2 cbloropropane isopropyl chloride, 1-chlorobutane, Sec-Butyl Chloride, 1- chloro-2-methyl propane and
1-chloropentane.
As bromine series solvent, for example, methylene bromide, Bromofume, tetrabromoethane, isopropyl bromide, n-propyl can be enumerated
Bromine, bromochloromethane and the bromo- 1,1- Difluoroethane of 1,2- bis-.
As fluorine series solvent, CH can be enumerated3CClF2、CH3CCl2F、CF3CF2CCl2H、CF2ClCF2The hydrogen chlorine of CFHCl etc.
Fluothane；
CF2ClCFClCF2CF3、CF3CFClCFClCF3Deng chlorofluoromethane；With
Freon C318, CF3CF2CF2CF3、CF3CF2CF2CF2CF3、CF3CF2CF2CF2CF2CF3Deng perfluoro alkane.
The reaction dissolvent can be used alone, or can also combine two or more use.The reaction dissolvent is more preferable
For methylene chloride, chloroform, carbon tetrachloride, methylene bromide, Bromofume or their mixed solvent of more than two kinds.
, it is surprising that in process A, when using methylene chloride as solvent, compared with the bromination of methylene chloride, on
The bromination high-priority for stating 1,1,2- tri- halogen ethane shown in formula (1) carries out, and obtains 1,1,2- tribromoethane.Due to methylene chloride
It can obtain at a low price, therefore, use methylene chloride to be advantageous in cost as solvent.
In the case that the raw material compound of process A is 1,1,2- trichloroethanes, 1,1,2- is obtained from extra high yield
From the viewpoint of tribromoethane, which is preferably bromine series solvent, only has the halogenated of bromine atom more preferably as halogen atom
Alkyl solvents, particularly preferred methylene bromide.
When implementing process A under conditions of there are reaction dissolvent, relative to 1,1,2- tri- halogen ethane shown in above-mentioned formula (1)
1 parts by weight, range of the amount of the reaction dissolvent preferably in the range of 3~30 parts by weight, more preferably in 3~10 parts by weight
It is interior.
In the case that the raw material compound of process A is the bromo- 1- chloroethanes of 1,2- bis-, process A preferably exists as reaction
Under conditions of the halogenated alkyl of solvent, implemented with following temperature condition: the upper limit of reaction temperature is preferably 20 DEG C, more preferably
10 DEG C, further preferably 0 DEG C；Preferably -78 DEG C of the lower limit of reaction temperature, more preferably -60 DEG C, further preferably -
40℃。
In the case that the raw material compound of process A is 1,1,2- trichloroethanes, process A preferably exists as reaction dissolvent
Halogenated alkyl (preferably bromine series solvent, only has the halo-alkyl solvents of bromine atom more preferably as halogen atom, particularly preferred two
Bromomethane) under conditions of, implemented with following temperature condition: the upper limit of reaction temperature is preferably 20 DEG C, and more preferably 10 DEG C, into
One step is preferably 5 DEG C；The lower limit of reaction temperature is preferably -78 DEG C, more preferably -50 DEG C, further preferably -30 DEG C.
Process A is preferably carried out under inactive gas.
As inactive gas, nitrogen etc. can be enumerated.
The manufacturing method of tri- halogen ethane of 1,1,2- shown in above-mentioned formula (1) used in process A is as described later.
An example of specific embodiment as process A can be enumerated in the aluminium and reaction dissolvent being added in reactor
The reaction dissolvent solution of bromine is added dropwise, the side of the reaction dissolvent solution of 1,1,2- tri- halogen ethane shown in above-mentioned formula (1) is then added dropwise
Method.
Another example of specific embodiment as process A can be enumerated in the aluminium and above-mentioned formula (1) being added in reactor
Shown in the method for bromine is added dropwise in tri- halogen ethane of 1,1,2-.
The another example of specific embodiment as process A can be enumerated and is added shown in above-mentioned formula (1) in the reactor
1,1,2- tri- halogen ethane, reaction dissolvent and bromine, after they are mixed, method that aluminium is added.
The another example of specific embodiment as process A can be enumerated in the aluminium bromide that is added in reactor and anti-
Answer the method that tri- halogen ethane of 1,1,2- shown in above-mentioned formula (1) is added dropwise in solvent.
An example again of specific embodiment as process A can be enumerated and is added shown in above-mentioned formula (1) in the reactor
1,1,2- tri- halogen ethane and reaction dissolvent after mixing them, add the method for aluminium and bromine (for example, carrying out 3 times (3 several times
Group) be respectively as defined in additive amount 1/3 amount aluminium addition and bromine dropwise addition method).
The manufacturing method of 1,1- dibromoethylene
The manufacturing method of 1,1- dibromoethylene of the invention includes the 1,1,2- tribromo that will pass through aforementioned present invention using alkali
1,1,2- tribromoethane dehydrobromination that the manufacturing method of ethane obtains obtains the process B of 1,1- dibromoethylene.
It can be direct by the 1,1,2- tribromoethane that the manufacturing method of the 1,1,2- tribromoethane of aforementioned present invention obtains
Essence is carried out for process B, or by customary ways such as solvent extraction, drying, filtration, distillation, concentration or their combinations
Process B is used for after system.
As alkali, for example, the inorganic base of sodium hydroxide, potassium hydroxide and magnesium hydroxide etc. can be enumerated；Sodium carbonate, carbonic acid
The inorganic alkaline salt of potassium, cesium carbonate, calcium carbonate and sodium bicarbonate etc.；And amine compounds are (for example, Armeen, aliphatic
Secondary amine, aliphatic tertiary amine, ester ring type secondary amine, ester ring type tertiary amine, aromatic amine, hetero ring type amine and polymer hold amine compounds)
Deng organic base.As the amine compounds, can enumerate in the aftermentioned amine compounds illustrated as stabilization agent.As aftermentioned steady
The amine compounds for determining agent can be used as the alkali and play a role.
Sodium hydroxide, potassium hydroxide, ammonia and triethylamine etc. is for example preferably listed as the alkali.
The alkali can be used alone, or can also combine two or more use.The combination for example can be inorganic base
With the combination of the amine compounds illustrated as aftermentioned stabilization agent.
The alkali (for example, sodium hydrate aqueous solution, ammonium hydroxide) can be used in the form of aqueous solution.The water of the aqueous solution can be with
It plays a role as reaction dissolvent.
Relative to 1,1,2- tribromoethane, the amount of the alkali preferably in the range of 0.9 equivalent~5.0 equivalent, more preferably exists
In the range of 0.9 equivalent~3.0 equivalents, further preferably in the range of 0.9 equivalent~2.0 equivalent, still more preferably exist
In the range of 1.0 equivalents~1.5 equivalents, more preferably in the range of 1.0 equivalents~1.2 equivalent.As described above, as stabilization
When the amine compounds that agent illustrates also are used as the alkali to play a role, preferably also the amount of the alkali including the amine compounds is such
Amount.
The upper limit of the reaction temperature of process B is preferably 100 DEG C, more preferably 80 DEG C, further preferably 60 DEG C.
The lower limit of the reaction temperature of process B is preferably 0 DEG C, more preferably 5 DEG C, further preferably 10 DEG C.
The reaction temperature of process B is preferably in the range of 0 DEG C~100 DEG C, more preferably in the range of 5 DEG C~80 DEG C, into
One step is preferably in the range of 10 DEG C~60 DEG C.
The reaction time of process B is usually in the range of 0.5~40 hour.
Process B can preferably be implemented in the presence of stabilization agent.In this specification, " stabilization agent " can be " polymerization inhibitor
Agent ", " anti-decomposition agent " are " polymerization inhibitor " and are " anti-decomposition agent ".Stabilization agent can be before the reaction of process B and in reaction
It is any at the time of add in the reaction system.In addition, implement before process B, work should be can be " before the reaction of process B "
Before the reaction of sequence A and reaction in it is any at the time of.
By implementing process B in the presence of stabilization agent, 1, the 1- dibromo second of the product as process B can be improved
The stability of alkene.
As the stabilization agent, for example, it is preferable to which it is secondary to enumerate Armeen, secondary aliphatic amine, aliphatic tertiary amine, ester ring type
Amine, ester ring type tertiary amine, aromatic amine, hetero ring type amine and polymer hold amine compounds of amine compounds etc. etc..
As Armeen, for example, methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, cyclohexylamine and second can be enumerated
Diamines.
As secondary aliphatic amine, for example, dimethylamine, diethylamine, di-n-propylamine, dibutyl amine, diamylamine, dihexylamine can be enumerated
And dicyclohexyl amine.
As aliphatic tertiary amine, for example, trimethylamine, triethylamine, diisopropyl ethyl amine, tri-n-butylamine and N, N can be enumerated,
N', N'- tetramethylethylenediamine.
As ester ring type secondary amine, for example, piperidines, piperazine, pyrrolidines, morpholine can be enumerated.
As ester ring type tertiary amine, for example, can enumerate N methyl piperazine, N- crassitude, 5- diazacyclo
4.3.0 ] nonyl- 5- alkene and 1,4- diazacyclo [ 2.2.2 ] octane.
As aromatic amine, for example, aniline, methylaniline, dimethylaniline, n,N-Dimethylaniline, halogen can be enumerated
For aniline and nitroaniline.
As hetero ring type amine, for example, pyridine, melamine, pyrimidine, piperazine, quinoline and imidazoles can be enumerated.
Amine compounds are held as polymer, for example, polyallylamine and polyvinyl pyridine can be enumerated.
In addition, can enumerate and be selected from down as stabilization agent other than the above (that is, stabilization agent other than amine compounds)
One or more of column compound (in this specification, the group is known as compound group (C) sometimes) compound (in this specification,
The compound is sometimes known as compound (C)).
(1) with hydroxyl compound,
(2) with thioether bond compound,
(3) compound with thiophenol or mercaptan sulphur atom,
(4) hydrosulfide and
(5) nitrous compound.
The compound (C) can be used alone, or can also combine two or more use.
As above-mentioned " compound that (1) has hydroxyl ", for example, methanol, ethyl alcohol, isopropanol and tert-butyl alcohol etc. can be enumerated
Formula: in the R-OH(formula, R for example indicates the alkyl of carbon atom number 1~6) shown in alcohol；And phenol quinhydrones, 4- methoxyl group
Phenol, DBH 2,5 di tert butylhydroquinone, methylnaphthohydroquinone, tert-butyl hydroquinone (TBH), 1,4-benzoquinone, methyl-p-benzoquinone, tert-butyl are to benzene
Quinone, 2,5- diphenyl 1,4-benzoquinone and 2,6 di tert butyl 4 methyl phenol (BHT) etc., with the hydroxyl by 1 or more
(here, which can be formed as oxygroup (O=) to the compound of the part-structure of substituted phenyl ring by tautomerism.The change
The carbon atom number for closing object is preferably 6~20) (hereinafter, the compound is referred to as phenolic compounds sometimes).
As above-mentioned " compound that (2) have thioether bond ", for example, can enumerate with dialkyl sulfide (this 2 " alkane
The carbon atom number of base " is identical or different, preferably 1~6) and the compound of diphenylsulfide structure (for example, diphenylsulfide and
Phenthazine etc., with aralkyl sulfid structure, carbon atom number 6~20, with thioether bond compound).
As above-mentioned " compound that (3) have thiophenol or mercaptan sulphur atom ", for example, can enumerate benzenethiol,
The R(-SH of dimercaptobenzene, 1,2- dimercaptoethylsulfide and 1,3- propanedithiol etc.)n[ in the formula, R for example indicates carbon atom
The alkane of number 1~6 or the aromatic carbon ring (for example, benzene, biphenyl) of carbon atom number 6~12；And n for example indicates integer 1 or 2 ] institute
The compound shown.
As above-mentioned " (4) hydrosulfide ", for example, can enumerate potassium sulfite, calcium sulfite, sodium hydrogensulfite,
Sodium sulfite, barium sulfite, magnesium sulfite, dimethyl sulfite, sulfurous acid diethyl ester, diamyl sulfite, sulfurous acid dipropyl
Ester and sulfurous acid diisopropyl ester.
As above-mentioned " (5) nitrous compound ", for example, can enumerate potassium nitrite, sodium nitrite, methyl nitrite,
Nitrous ether (ethyl nitrite), amyl nitrite, propyl nitrite and Isopropyl Nitrite.
The above-mentioned compound (C) as stabilization agent is preferably above-mentioned " compound that (1) has hydroxyl ", more preferably
Phenolic compounds.
As aforementioned stable agent, for example, it is preferable to enumerate diisopropyl ethyl amine, tri-n-butylamine, triethylamine, 4- methoxyl group
Phenol, 2,6 di tert butyl 4 methyl phenol (BHT), pyridine, melamine and phenthazine etc..
The stabilization agent can be used alone, or can also combine two or more use.
In a preferred mode of the invention, process B it is can playing a role respectively as stabilization agent, (1) a kind
Implement in the presence of above amine compounds and (2) 1 kinds or more of compound (C).
When using stabilization agent in process B, relative to 1,1,2- tribromoethane, total amount is preferably in 100~50000ppm
(w/w) in the range of, more preferably in 100~10000ppm(w/w) in the range of, further preferably in 100~3000ppm(w/
W) in the range of, still more preferably in 100~3000ppm(w/w) in the range of, particularly preferably in 500~2000ppm(w/
W) in the range of, further particularly preferably in 500~1500ppm(w/w) in the range of.
It plays a role as described above, the amine compounds as aforementioned stable agent can also be used as above-mentioned alkali, it is steady existing
When determining to implement under conditions of agent process B, preferably by the inorganic base as alkali and appropriate group of amine compounds as stabilization agent
It closes and uses.Wherein, here, it plays a role within the scope of the invention as the amine compounds of stabilization agent as alkali, another party
Face, the amine compounds as alkali play a role also within the scope of the invention as stabilization agent.
In a particularly preferred embodiment of the invention, 1 generated in process A, the purification of 1,2- tribromoethane
Afterwards, a kind or more of amine compounds are wherein being added, obtained composition is being used in process B.
The reaction of process B is preferably implemented under conditions of there are reaction dissolvent.
As the reaction dissolvent, for example, the mixing of more than two kinds that can enumerate water-soluble solvent and water and they is molten
Agent.
The reaction dissolvent is preferably the mixed solvent of water-soluble solvent or water-soluble solvent and water.Water-soluble solvent and water
Mixed solvent be the mixed solvent containing water-soluble solvent and water, can also be containing solvent in addition to this, preferably substantially
It is made of water-soluble solvent and water, is more preferably only made of water-soluble solvent and water.The in the mixed solvent, water can come from as above
The aqueous solution of the alkali.
As the reaction dissolvent or in the reaction dissolvent water-soluble solvent, for example, can enumerate: methanol, ethyl alcohol,
The alcohol of normal propyl alcohol, isopropanol, n-butanol and the tert-butyl alcohol etc.；The ketone of acetone and methyl ethyl ketone (MEK) etc.；Diethyl ether and tetrahydrofuran
(THF) the ether such as；And acetic acid, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethyl acetamide (DMAc) and
1-Methyl-2-Pyrrolidone (NMP) etc..
As the water-soluble solvent, preferably methanol, DMF, THF or NMP.
By using such solvent, the purification of 1,1- dibromoethylene obtained in process B can pass through washing etc.
It needs not move through distillation easily to carry out, also, thereby, it is possible to reduce the risk of the polymerization of 1,1- dibromoethylene.
Relative to 1 parts by weight of 1,1,2- tribromoethane, the amount of the reaction dissolvent is usually in the range of 0~20 parts by weight
It is interior, preferably in the range of 0.1~15 parts by weight, more preferably in the range of 0.1~10 parts by weight.
Process B there are water and be not present water-miscible organic solvent under conditions of implement when, it is preferable to use phase transfer catalysis (PTC)
Agent.The water can be the water of the aqueous solution of the water or above-mentioned alkali as above-mentioned " reaction dissolvent ".
As phase transfer catalyst, for example, can enumerate tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium bromide,
The quaternary ammonium salt of tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutyl ammonium sulfate and tri-n-octyl methyl ammonium chloride etc.；Tetrabutyl chlorination
The quaternary alkylphosphonium salt such as Phosphonium；The pyridine compounds of dodecyl pyridinium chloride etc.；And crown ether etc..
It is wherein for example preferably tetramethyl ammonium chloride or tetrabutylammonium bromide.
When using phase transfer catalyst, relative to 1,1,2- tribromoethane, amount is preferably in 0.01 equivalent~1 equivalent
In range, more preferably in the range of 0.01 equivalent~0.5 equivalent, further preferably in 0.01 equivalent~0.1 equivalent range
It is interior.
An example of specific embodiment as process B can be enumerated and utilize system of the invention in addition reactor
Make the method that the reaction dissolvent solution of alkali is added in the 1,1,2- tribromoethane, reaction dissolvent and stabilization agent of method manufacture.
The 1,1- dibromoethylene obtained by the manufacturing method can according to need pass through addition water and carry out liquid separation etc.,
Customary way is separated or is refined.
After the reaction of process B, stabilization agent can be added in product." after the reaction of process B " can refer to 1,1-
After the separation or purification of dibromoethylene.Stabilization agent is added in product after the reaction of process B in this way, can be improved
The storage stability of the product.As the stabilization agent, can enumerate and above-mentioned appointing before the reacting of process B and in reaction
The same substance of stabilization agent used at the time of meaning (that is, when the reaction of process B).
When all using stabilization agent in the reaction of process B and after the reaction of process B, generated after the reaction of process B
The stabilization agent added in object can in the reaction of process B used stabilization agent it is identical, can also be different.
From reactivity and stability from the viewpoint of, preferably after the reaction of the process B used stabilization agent with it is above-mentioned
Used stabilization agent is different when the reaction of process B.
In addition, similarly from the viewpoint of reactivity and stability, it is 2 kinds used preferably after the reaction of the process B
In above stabilization agent it is at least one kind of from the reaction of above-mentioned operation B used stabilization agent it is different.
1 kind or more of the amine compounds that can be played a role as stabilization agent are added more preferably before the reaction of process B,
Above-mentioned a kind or more of the compound (C) that can be played a role as stabilization agent is added after the reaction of process B.The compound
(C) preferably above-mentioned " compound that (1) has hydroxyl ", more preferably phenolic compounds.
Specifically, in a preferred mode of the invention, for example, Xiang Fanying before the reaction of process B or in reaction
System adds triethylamine, and adds in product (after the separation or purification of preferably 1,1- dibromoethylene) after the reaction of process B
Add BHT.
Relative to 1,1- dibromoethylene, the amount of the stabilization agent added in product after the reaction of process B preferably exists
100~3000ppm(w/w) in the range of, more preferably in 100~2000ppm(w/w) in the range of, further preferably 100~
In the range of 1500ppm(w/w).
In one embodiment of the present invention, process B is in a kind or more for capable of playing a role as stabilization agent in the presence of (1)
Amine compounds and (2) can be as above compound (the C) (preferably above-mentioned " change of (1) with hydroxyl that stabilization agent plays a role
Close object ", more preferable phenolic compounds) under conditions of implement.
Wherein, preferable process B is there are a kind or more of amine compounds and 2,6- di-tert-butyl-4-methy phenols
(BHT) implement under conditions of.
In the reaction of process B, the compound (C) of (1) a kind or more of amine compounds and above-mentioned a kind of (2) or more is (on preferably
State the compound of hydroxyl " (1) have ", more preferable phenolic compounds, particularly preferred BHT) can respectively before the reaction of process B and
In reaction it is any at the time of (that is, when the reaction of process B) added into reaction system, preferably added before the reaction of process B.
The reaction is novel.
Relative to 1,1- dibromoethylene, the amount of a kind or more of the amine compounds added in the reaction system of process B in this way
It is preferred that in 100~50000ppm(w/w) in the range of, more preferably in 100~10000ppm(w/w) in the range of, it is further excellent
It is selected in 100~3000ppm(w/w) in the range of, still more preferably in 100~2000ppm(w/w) in the range of, it is especially excellent
It is selected in 100~1500ppm(w/w) in the range of.
Relative to 1,1- dibromoethylene, a kind or more of above compound being added in the reaction system of process B in this way
(C) (preferably above-mentioned the compound of hydroxyl " (1) have ", more preferable phenolic compounds, particularly preferred BHT)) amount preferably 100~
In the range of 50000ppm(w/w), more preferably in 100~10000ppm(w/w) in the range of, further preferably 100~
In the range of 3000ppm(w/w), still more preferably in 100~2000ppm(w/w) in the range of, particularly preferably 100~
In the range of 1500ppm(w/w).
In addition, as 1, other methods of 1- dibromoethylene, the system with above explained 1,1- dibromoethylene of the invention
Method is made equally to operate, but it is also possible to by replace 1,1,2- tribromoethane, use (1) 1,1,1- tribromoethane or (2) 1,
1,2- tribromoethane and 1,1,1- tribromoethane manufacture.
Specifically, 1,1- dibromoethylene is for example manufactured by manufacturing method described below.
The manufacturing method of the 1,1- dibromoethylene includes using alkali by 1,1,2- tribromoethane and/or 1,1,1- tribromoethane
Dehydrobromination, the process for obtaining 1,1- dibromoethylene.
For the process, when by arbitrary at the time of any, i.e. before the reaction of the process, after reaction neutralization reaction
It carves into reaction system or reaction product and to add (1) a kind or more of amine compounds and (2) 1 kinds or more of above-mentioned chemical combination respectively
Object (C) can manufacture 1,1- dibromoethylene composition of the invention.
The mode of addition as (1) a kind or more of amine compounds and (2) 1 kinds or more of above compound (C), for example,
It may be exemplified:
From the mode of initial phase of above-mentioned operation (this includes " before the reaction of above-mentioned operation ") addition both sides,
(this includes " above-mentioned operation after since the initial phase of above-mentioned operation adds a side, the reaction in above-mentioned operation
After reaction ") addition another party mode,
Since the initial phase of above-mentioned operation add a side, above-mentioned operation reaction after add both sides mode (that is,
The mode further added for above-mentioned " side "),
The initial phase of above-mentioned operation do not add it is any, after the completion of reaction add both sides modes,
The initial phase of above-mentioned operation do not add it is any, in the reaction at the same add both sides mode and
The initial phase of above-mentioned operation do not add it is any, in the reaction respectively add both sides mode.
1,1,1- tribromoethane can be manufactured by well known method or based on its method.
The manufacturing method of the bromo- 1- chloroethanes of 1,2- bis-
As described above, the bromo- 1- chloroethanes of 1,2- bis- used in process A is for example fitted through including making vinyl chloride addition
The method of the process C of bromine manufactures.
It for example can be by implementing vinyl chloride with bromine reaction to vinyl chloride addition bromine.
Relative to vinyl chloride, the amount of bromine preferably in the range of 0.9 equivalent~2.0 equivalent, more preferably 1.0 equivalents~
1.5 in the range of equivalent, further preferably in the range of 1.0 equivalents~1.1 equivalent.
The upper limit of the reaction temperature of process C is preferably 55 DEG C, more preferably 40 DEG C, further preferably 30 DEG C.
The lower limit of the reaction temperature of process C is preferably -5 DEG C, more preferably 0 DEG C, further preferably 5 DEG C.
The reaction temperature of process C is preferably in the range of -5 DEG C~55 DEG C, more preferably in the range of 0 DEG C~40 DEG C, into
One step is preferably in the range of 5 DEG C~30 DEG C.
The reaction time of process C is usually in the range of 1~20 hour.
Process C can be there are reaction dissolvent or there is no implement under conditions of reaction dissolvent.
The solvent is, for example, carbon tetrachloride, chloroform and their mixed solvent.
The example of specific embodiment as process C can be enumerated and be led in the reactor that joined bromine by being bubbled
The method for entering or being pressed into vinyl chloride.
When being pressed into vinyl chloride, the pressure (internal pressure) (gauge pressure) in reactor preferably in the range of 0.01MPa~0.3MPa,
More preferably in the range of 0.05MPa~0.25MPa, further preferably in the range of 0.05MPa~0.2MPa.
The bromo- 1- chloroethanes of 1,2- bis- obtained by the manufacturing method can be directly used for process A, or pass through vacuum distillation
Or the conventional processes such as concentration refined after for process A.
Embodiment
Hereinafter, the present invention is described in more detail by embodiment, but the present invention is not limited thereto.
In embodiment below, gas chromatographic method (GC) is implemented according to following GC condition.
< GC condition >
GC device: SHIMADZU GC-2010
Column: J&W DB-5MS(0.25 μm, 60m, 0.25mmID)
Post case: 40 DEG C (4 minutes) → heating (10 DEG C/min) → 300 DEG C (0 minute)
Gasify room temperature: 200 DEG C
Embodiment C1
Bromine (50g, 315mmol) is added in the reactor for having blender, be pressed into while cooling vinyl chloride (21.5g,
344mmol).Hereafter it is warming up to room temperature, stirs 17 hours overnight, reaction was completed.By being evaporated under reduced pressure to obtained crude product
It is refined, 1,2-, bis- bromo- 1- chloroethanes (67.6g, yield 97%) is obtained in the form of colorless oil.
Embodiment C2
Bromine (500g, 3.13mol) is added in the reactor, vinyl chloride add while cooling until bromine color disappearance, with
The form of colorless oil obtains 1,2-, bis- bromo- 1- chloroethanes (696.5g, yield 100%).
Embodiment A1
After carrying out nitrogen displacement in reactor, aluminium (109mg, 4.05mmol) and methylene chloride (30mL) is added.Side stirring
While being cooled to -20 DEG C, methylene chloride (20mL) solution of bromine (1.07g, 6.75mmol) is added dropwise.It is stirred 15 minutes at -20 DEG C
Afterwards, methylene chloride (20mL) solution of the bromo- 1- chloroethanes (3g, 13.5mmol) of 1,2- bis- is added dropwise.It is stirred 1 hour with -20 DEG C
Afterwards, it is injected into ice water.Liquid separation is slightly carried out after stirring, obtains 1,1,2- tribromoethane (GC area 74%), and recycle work
For the bis- bromo- 1- chloroethanes (GC area 20%) of 1,2- of raw material.
Embodiment A2
The equivalent for being changed to 0.4, bromine relative to the equivalent of the aluminium of the bromo- 1- chloroethanes of 1,2- bis- is changed to 0.65, removes this
It is same as embodiment A1 in addition to operate, 1,1,2- tribromoethane (GC area 89%) is obtained, and recycle 1, the 2- bis- as raw material
Bromo- 1- chloroethanes (GC area 9%).
Embodiment A3
The weight ratio of the bromo- 1- chloroethanes of 1,2- bis- and methylene chloride is changed to 1:10(here, 1,2- bis- bromo- 1- chloroethene
The amount of alkane is identical as embodiment A1), it is same as embodiment A1 in addition to this to operate, obtain 1,1,2- tribromoethane (GC area
73%), and 1,2-, bis- bromo- 1- chloroethanes (GC area 26%) as raw material is recycled.
Embodiment A4
The equivalent for being changed to 0.5, bromine relative to the equivalent of the aluminium of the bromo- 1- chloroethanes of 1,2- bis- is changed to 0.8, by 1,2-
The weight ratio of two bromo- 1- chloroethanes and methylene chloride is changed to 1:10(here, the amount and embodiment of 1,2- bis- bromo- 1- chloroethanes
A1 is identical), it is same as embodiment A1 in addition to this to operate, 1,1,2- tribromoethane (GC area 97%) is obtained, and recycle conduct
The bis- bromo- 1- chloroethanes (GC area 2%) of 1,2- of raw material.
Embodiment A5
The equivalent for being changed to 0.5, bromine relative to the equivalent of the aluminium of the bromo- 1- chloroethanes of 1,2- bis- is changed to 0.5, by 1,2-
The weight ratio of two bromo- 1- chloroethanes and methylene chloride is changed to 1:10(here, the amount and embodiment of 1,2- bis- bromo- 1- chloroethanes
A1 is identical), it is same as embodiment A1 in addition to this to operate, 1,1,2- tribromoethane (GC area 89%) is obtained, and recycle conduct
The bis- bromo- 1- chloroethanes (GC area 5%) of 1,2- of raw material.
Embodiment A6
Reaction temperature is changed to 0 DEG C, it is same as embodiment A1 in addition to this to operate, obtain 1,1,2- tribromoethane (GC
Area 20%), the bromination bodies (GC area 37%) of two sym-chlorobromoethanes (GC area 14%) and methylene chloride, and recycle as original
The bis- bromo- 1- chloroethanes (GC area 29%) of 1,2- of material.
Embodiment A7
After carrying out nitrogen displacement in reactor, it is added aluminium (60.7mg, 2.25mmol) and 1, the bromo- 1- chloroethanes of 2- bis- (1g,
4.5mmol).It is cooled to -20 DEG C while stirring, is added dropwise bromine (360mg, 2.25mmol).After being stirred 1 hour with -20 DEG C, injection
Into ice water.Liquid separation is slightly carried out after stirring, obtains 1,1,2- tribromoethane (GC area 48%), and recycle as raw material
Bis- bromo- 1- chloroethanes (GC area 52%) of 1,2-.
Embodiment A8
It is same as embodiment A7 to operate other than it will be changed to 5.5 hours the reaction time, obtain 1,1,2- tribromoethane
(GC area 90%), and recycle 1,2-, the bis- bromo- 1- chloroethanes (GC area 0.3%) as raw material.
Embodiment A9
After carrying out nitrogen displacement in reactor, it is added aluminium (60mg, 2.25mmol) and 1,2- dichloroethanes (8mL).While stirring
It mixes side and is cooled to -20 DEG C, be added dropwise bromine (360mg, 2.25mmol).After stirring 15 minutes with -20 DEG C, the bromo- 1- of 1,2- bis- is added dropwise
Chloroethanes (1g, 4.5mmol).After being stirred 1 hour with -20 DEG C, it is injected into ice water.Liquid separation is slightly carried out after stirring, is obtained
1,1,2- tribromoethane (GC area 32%) and 1, the bromination body (GC area 30%) of 2- dichloroethanes, and recycle as raw material
Bis- bromo- 1- chloroethanes (GC area 34%) of 1,2-.
Embodiment A10
After carrying out nitrogen displacement in reactor, aluminium bromide (396mg, 1.49mmol) and methylene chloride (7.6mL) is added.Side
Stirring side is cooled to -20 DEG C, and the bromo- 1- chloroethanes (1g, 4.5mmol) of 1,2- bis- is added dropwise.After being stirred 1 hour with -20 DEG C, injection
Into ice water.Liquid separation is slightly carried out after stirring, obtains 1,1,2- tribromoethane (GC area 92%).
Embodiment A11
After carrying out nitrogen displacement in reactor, aluminium (60.7mg, 2.25mmol) and methylene bromide (30g) is added.Side stirring
While being cooled to 0 DEG C, it is added dropwise bromine (360mg, 2.25mmol).After stirring 15 minutes with 0 DEG C, the bromo- 1- chloroethanes of 1,2- bis- is added dropwise
(1g, 4.5mmol).After being stirred 1 hour with 0 DEG C, it is injected into ice water.Liquid separation is slightly carried out after stirring, obtains 1,1,2- tri-
Bromoethane (GC area 82%), and recycle 1,2-, the bis- bromo- 1- chloroethanes (GC area 2%) as raw material.
Embodiment A12
After carrying out nitrogen displacement in reactor, aluminium (240mg, 8.90mmol) and methylene bromide (30g) is added.While stirring
- 20 DEG C are cooled to, is added dropwise bromine (1.8g, 11.3mmol).After stirring 15 minutes with -20 DEG C, 1,1,2- trichloroethanes is added dropwise
(1g, 7.50mmol).After being warming up to 0 DEG C, stirring 5.5 hours, it is injected into ice water.Liquid separation is slightly carried out after stirring, is obtained
1,1,2- tribromoethane (GC area 88%), chlorine Bromofume (GC area 2%) and a variety of unknown objects of structure, and recycle work
For the 1,1,2- trichloroethanes (GC area 5%) of raw material.
Embodiment A13
After carrying out nitrogen displacement in reactor, the bromo- 1- chloroethanes (50g, 225mmol) of 1,2- bis-, methylene chloride is added
(250g), bromine (19.8g, 125mmol).It is cooled to -10 DEG C while stirring, adds aluminium (2.43g, 90mmol).Keep the temperature
After stirring 1 hour, it is injected into ice water.Liquid separation is slightly carried out after stirring, obtains 1,1,2- tribromoethane (GC area
84%), and 1,2-, bis- bromo- 1- chloroethanes (GC area 15%) as raw material is recycled.
Embodiment A14
After carrying out nitrogen displacement in reactor, the bromo- 1- chloroethanes (1000g, 3.75mol) of 1,2- bis-, methylene chloride is added
(4000mL).It is cooled to -20 DEG C, after addition aluminium (20.3g, 752mmol) while stirring, is added dropwise bromine (192g, 1.20mol).It should
Addition operation is total to be carried out 3 times.After keeping the temperature to stir 3 hours, it is injected into ice water.Liquid separation is slightly carried out after stirring,
Obtain crude product.By carrying out distillation purification to obtained crude product, 1,1,2- tribromoethane (yield 94%, GC is obtained
Area 99%).
Embodiment B1
Methanol (0.3g), 1,1,2- tribromoethane (3.0g, 11.2mmol), Et are added in the reactor3N(5mg).Again plus
After entering 25% sodium hydrate aqueous solution (1.97g, 12.3mmol), warming while stirring is to 50 DEG C.The temperature is kept to stir 20 hours
Afterwards, liquid separation is carried out, 1,1- dibromoethylene (1.68g, yield 81%, GC area 98.7%) is obtained in the form of colorless oil.
Embodiment B2
DMF(1g is added in the reactor), 1,1,2- tribromoethane (1.0g, 3.75mmol), Et3N(1mg).Hydrogen is added
After sodium oxide molybdena (165.2mg, 4.13mmol), warming while stirring is to 50 DEG C.After reaction, water is added and carries out liquid separation, with
The form of colorless oil obtains 1,1- dibromoethylene (GC area 96.5%).
Embodiment B3
THF(1g is added in the reactor), 1,1,2- tribromoethane (1.0g, 3.75mmol), Et3N(1mg).Hydrogen is added
After sodium oxide molybdena (165.2mg, 4.13mmol), warming while stirring is to 50 DEG C.After reaction, water is added and carries out liquid separation, with
The form of colorless oil obtains 1,1- dibromoethylene (GC area 95.4%).
Embodiment B4
NMP(1g is added in the reactor), 1,1,2- tribromoethane (1.0g, 3.75mmol), Et3N(1mg).Hydrogen is added
After sodium oxide molybdena (165.2mg, 4.13mmol), warming while stirring is to 50 DEG C.After reaction, water is added and carries out liquid separation, with
The form of colorless oil obtains 1,1- dibromoethylene (GC area 92.4%).
Embodiment B5
Methanol (0.5g), 1,1,2- tribromoethane (5.0g, 18.7mmol), Et are added in the reactor3N(189mg,
1.87mmol).It is added in the mixed solution 50% sodium hydrate aqueous solution (1.65g, 20.6mmol), it is small to be stirred at room temperature 15
When.It is analyzed using NMR and GC, obtains 1,1- dibromoethylene (yield 94%).
Embodiment B6
Methanol (0.5g), 1,1,2- tribromoethane (5.0g, 18.7mmol), Et are added in the reactor3N(5mg).At this
50% sodium hydrate aqueous solution (1.65g, 20.6mmol) is added in mixed solution, to be stirred at room temperature 15 hours.Utilize NMR and GC
It is analyzed, obtains 1,1- dibromoethylene (yield 91%, GC area 98.8%).
Embodiment B7
In the reactor be added tetramethyl ammonium chloride (205.5mg, 1.875mmol), 1,1,2- tribromoethane (10g,
37.5mmol), Et3N(10mg).After 50% sodium hydrate aqueous solution of ice-cold lower addition (3.3g, 41.3mmol), stirred with room temperature
Liquid separation is carried out after mixing 51 hours, 1,1- dibromoethylene (GC area 56%) is obtained in the form of colorless oil.
Industrial utilizability
The 1,1,2- tribromoethane and 1,1- dibromoethylene that manufacturing method through the invention obtains be as medicine (such as
Antibiotic) synthetic intermediate, the synthetic intermediate of outsourcing material of optical fiber, coating material synthetic intermediate,
The useful compound such as the synthetic intermediate of monomer of synthetic intermediate and functional high-polymer of semiconductor corrosion resistant material.
Claims (8)
1. one kind 1,1, the manufacturing method of 2- tribromoethane, it is characterised in that:
Including tri- halogen ethane of 1,1,2- shown in formula (1) and aluminium and bromine reaction or with the halogenation with 1 or more bromine atom
Reactive aluminum and obtain 1, the process A of 1,2- tribromoethane,
The reaction temperature of the process A at 0 DEG C hereinafter,
In formula, X1、X2And X3Indicate chlorine atom or bromine atom, wherein X1、X2And X3Middle at least one is chlorine atom.
2. manufacturing method as described in claim 1, it is characterised in that:
Tri- halogen ethane of 1,1,2- shown in the formula (1) is the bromo- 1- chloroethanes of 1,2- bis- or 1,1,2- trichloroethanes.
3. manufacturing method as described in claim 1, it is characterised in that:
The aluminum halide for having 1 or more bromine atom is aluminium bromide.
4. manufacturing method according to any one of claims 1 to 3, it is characterised in that:
The reaction temperature of process A is in the range of -78 DEG C~0 DEG C.
5. manufacturing method according to any one of claims 1 to 3, it is characterised in that:
Process A is implemented under conditions of there are the halogenated alkyl compounds as reaction dissolvent.
6. one kind 1, the manufacturing method of 1- dibromoethylene characterized by comprising
Tri- halogen ethane of 1,1,2- shown in formula (1) is anti-with aluminium and bromine reaction or with the aluminum halide with 1 or more bromine atom
It answers and obtains the process A of 1,1,2- tribromoethane, and
1,1, the 2- tribromoethane dehydrobromination that will be obtained by the process A using alkali, the process for obtaining 1,1- dibromoethylene
B,
Wherein, the reaction temperature of the process A at 0 DEG C hereinafter,
In formula, X1、X2And X3Indicate chlorine atom or bromine atom, wherein X1、X2And X3Middle at least one is chlorine atom.
7. manufacturing method as claimed in claim 6, it is characterised in that:
There is the item as the water-miscible organic solvent or water-miscible organic solvent of reaction dissolvent and the mixed solvent of water in process B
Implement under part.
8. manufacturing method as claimed in claim 6, it is characterised in that:
Process B is there are water and water-miscible organic solvent is not present under conditions of is implemented using phase transfer catalyst.
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| JP2014092900 | 2014-04-28 | ||
| JP2014-092900 | 2014-04-28 | ||
| JP2015-012505 | 2015-01-26 | ||
| JP2015-012510 | 2015-01-26 | ||
| JP2015012510A JP5987926B2 (en) | 2014-04-28 | 2015-01-26 | Composition |
| JP2015012505A JP5900671B2 (en) | 2014-04-28 | 2015-01-26 | Process for producing 1,1,2-tribromoethane |
| PCT/JP2015/062878 WO2015166961A1 (en) | 2014-04-28 | 2015-04-28 | 1,1,2-tribromoethane production method |
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| CN201911300719.6A Pending CN111138241A (en) | 2014-04-28 | 2015-04-28 | 1, 1-dibromoethylene composition |
| CN201580022827.5A Active CN106255675B (en) | 2014-04-28 | 2015-04-28 | Composition comprising a metal oxide and a metal oxide |
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| US1891415A (en) * | 1930-04-09 | 1932-12-20 | Dow Chemical Co | Preparation of brominated hydrocarbons |
| JPS5052006A (en) * | 1973-09-13 | 1975-05-09 | ||
| JPS59108727A (en) * | 1982-11-29 | 1984-06-23 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Improved dehalogenation hydrogenation |
| JP2013519631A (en) * | 2010-02-19 | 2013-05-30 | ダイキン工業株式会社 | Process for producing 2-chloro-3,3,3-trifluoropropene |
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| JPS6456637A (en) * | 1987-08-25 | 1989-03-03 | Toso Yuki Kagaku Kk | Production of 3-bromobenzaldehyde |
| JPH1072383A (en) * | 1996-09-03 | 1998-03-17 | Tosoh Corp | Stabilization of allyl bromide and stabilized allyl bromide composition |
| JP5360806B2 (en) * | 2008-11-11 | 2013-12-04 | 独立行政法人産業技術総合研究所 | Method for producing fluorinated cyclobutane compound |
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| JP2015012510A (en) * | 2013-06-28 | 2015-01-19 | 株式会社新日本電波吸収体 | Rfid antenna cell and system |
| RU2670757C2 (en) * | 2013-09-03 | 2018-10-25 | Дайкин Индастриз, Лтд. | Method for producing 1,1-dibromo-1-fluoroethane |
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2015
- 2015-01-26 JP JP2015012505A patent/JP5900671B2/en active Active
- 2015-01-26 JP JP2015012510A patent/JP5987926B2/en active Active
- 2015-04-28 CN CN201580022949.4A patent/CN106458797B/en active Active
- 2015-04-28 CN CN201911300719.6A patent/CN111138241A/en active Pending
- 2015-04-28 CN CN201580022827.5A patent/CN106255675B/en active Active
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| US1891415A (en) * | 1930-04-09 | 1932-12-20 | Dow Chemical Co | Preparation of brominated hydrocarbons |
| JPS5052006A (en) * | 1973-09-13 | 1975-05-09 | ||
| JPS59108727A (en) * | 1982-11-29 | 1984-06-23 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Improved dehalogenation hydrogenation |
| JP2013519631A (en) * | 2010-02-19 | 2013-05-30 | ダイキン工業株式会社 | Process for producing 2-chloro-3,3,3-trifluoropropene |
Also Published As
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| CN106255675B (en) | 2021-12-03 |
| JP2015221779A (en) | 2015-12-10 |
| CN106255675A (en) | 2016-12-21 |
| CN111138241A (en) | 2020-05-12 |
| JP5900671B2 (en) | 2016-04-06 |
| CN106458797A (en) | 2017-02-22 |
| JP2015221778A (en) | 2015-12-10 |
| JP5987926B2 (en) | 2016-09-07 |
| JP2016164188A (en) | 2016-09-08 |
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