CN100497281C - Method of preparing p-bromophenyl ether - Google Patents
Method of preparing p-bromophenyl ether Download PDFInfo
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- CN100497281C CN100497281C CNB2007100203379A CN200710020337A CN100497281C CN 100497281 C CN100497281 C CN 100497281C CN B2007100203379 A CNB2007100203379 A CN B2007100203379A CN 200710020337 A CN200710020337 A CN 200710020337A CN 100497281 C CN100497281 C CN 100497281C
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- 238000000034 method Methods 0.000 title claims abstract description 89
- YAWIAFUBXXPJMQ-UHFFFAOYSA-N 1-bromo-4-(4-bromophenoxy)benzene Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1 YAWIAFUBXXPJMQ-UHFFFAOYSA-N 0.000 title 1
- 238000005893 bromination reaction Methods 0.000 claims abstract description 43
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000012545 processing Methods 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- JMSKYMHFNWGUJG-UHFFFAOYSA-N 1-bromo-2-(2-bromophenoxy)benzene Chemical compound BrC1=CC=CC=C1OC1=CC=CC=C1Br JMSKYMHFNWGUJG-UHFFFAOYSA-N 0.000 claims description 137
- 239000000203 mixture Substances 0.000 claims description 122
- 238000006277 sulfonation reaction Methods 0.000 claims description 100
- 239000012074 organic phase Substances 0.000 claims description 88
- 239000000243 solution Substances 0.000 claims description 85
- 238000002360 preparation method Methods 0.000 claims description 75
- 239000000463 material Substances 0.000 claims description 56
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 38
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052794 bromium Inorganic materials 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 239000008346 aqueous phase Substances 0.000 claims description 15
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 14
- 238000005292 vacuum distillation Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 125000001246 bromo group Chemical group Br* 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 241000282326 Felis catus Species 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 8
- 235000010333 potassium nitrate Nutrition 0.000 claims description 8
- 239000004323 potassium nitrate Substances 0.000 claims description 8
- 235000010289 potassium nitrite Nutrition 0.000 claims description 8
- 239000004304 potassium nitrite Substances 0.000 claims description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- 229940001516 sodium nitrate Drugs 0.000 claims description 8
- 235000010288 sodium nitrite Nutrition 0.000 claims description 8
- 239000003570 air Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical group OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 2
- IUILGHBUWUXVBP-UHFFFAOYSA-N (4-bromobenzoyl) 4-bromobenzoate Chemical compound C1=CC(Br)=CC=C1C(=O)OC(=O)C1=CC=C(Br)C=C1 IUILGHBUWUXVBP-UHFFFAOYSA-N 0.000 abstract 1
- XVZXORKCIPSWKZ-UHFFFAOYSA-N 5-bromo-7-oxabicyclo[4.1.0]hepta-1(6),2,4-triene Chemical compound BrC1=CC=CC2=C1O2 XVZXORKCIPSWKZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000002994 raw material Substances 0.000 description 16
- 238000007670 refining Methods 0.000 description 16
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000003822 preparative gas chromatography Methods 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 11
- 239000003814 drug Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 4
- -1 bromo aromatic ether Chemical class 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- JJFOBACUIRKUPN-UHFFFAOYSA-N 2-bromoethoxybenzene Chemical compound BrCCOC1=CC=CC=C1 JJFOBACUIRKUPN-UHFFFAOYSA-N 0.000 description 2
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 2
- RCDCLMITEHNUPV-UHFFFAOYSA-M [Na+].C1=CC=C(C=C1)S(=O)(=O)[O-].BrC1=C(C=CC=C1)OC Chemical compound [Na+].C1=CC=C(C=C1)S(=O)(=O)[O-].BrC1=C(C=CC=C1)OC RCDCLMITEHNUPV-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006353 environmental stress Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- HFEFLNNDSLOUEM-UHFFFAOYSA-N 1-bromo-2-butoxybenzene Chemical compound CCCCOC1=CC=CC=C1Br HFEFLNNDSLOUEM-UHFFFAOYSA-N 0.000 description 1
- JVEQWIQHHWNMQX-UHFFFAOYSA-N 1-bromo-2-ethoxybenzene Chemical compound CCOC1=CC=CC=C1Br JVEQWIQHHWNMQX-UHFFFAOYSA-N 0.000 description 1
- WPDXAMRGYMDTOV-UHFFFAOYSA-N 3-bromo-2-methylphenol Chemical compound CC1=C(O)C=CC=C1Br WPDXAMRGYMDTOV-UHFFFAOYSA-N 0.000 description 1
- NIDWUZTTXGJFNN-UHFFFAOYSA-N 3-bromopropoxybenzene Chemical compound BrCCCOC1=CC=CC=C1 NIDWUZTTXGJFNN-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- YFNONBGXNFCTMM-YMHOBSDZSA-N butoxybenzene Chemical group CCCCO[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 YFNONBGXNFCTMM-YMHOBSDZSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000005217 methyl ethers Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical group CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- DSNYFFJTZPIKFZ-UHFFFAOYSA-N propoxybenzene Chemical group CCCOC1=CC=CC=C1 DSNYFFJTZPIKFZ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a making method of bromoaromatic ether, which is characterized by the following: proceeding bromination reaction for phenyl ether and brominating agent under oxidant and accelerant to produce bromobenzene ether; adopting composite material as p-bromobenzoyl ether directly or processing composite material to obtain the product.
Description
Technical field
The invention belongs to the method for preparing the bromo aromatic ether, be specifically related to the method for a kind of preparation bromophenyl ether.
Background technology
To bromophenyl ether is a kind of synthetic intermediate of important medicine, agricultural chemicals or type material, so selectively synthetic have very important industrial significance to bromophenyl ether.A kind of traditional preparation is to make p bromophenol through alkylation and prepare bromophenyl ether to the method for bromophenyl ether, but the industrial preparation flow process of the raw materials used p bromophenol of this preparation method is comparatively complicated, and seriously polluted, cost is higher.Another kind of traditional preparation is that (bromine is industrial liquid bromine with phenyl ether and liquid bromine or bromine to the method for bromophenyl ether, liquid bromine mass percent therein is generally greater than 99.5%) directly bromination reaction takes place and prepare bromophenyl ether, can generate by product o-bromophenyl ether when phenyl ether and liquid bromine or bromine generation bromination reaction generate bromophenyl ether and hydrogen bromide in this method, and bromophenyl ether is difficult to separate with o-bromophenyl ether, cause the purity of bromophenyl ether finished product unsatisfactory; In addition, this directly bromination reaction takes place with phenyl ether and liquid bromine or bromine (being industrial liquid bromine) and prepare in the method to bromophenyl ether, because the hydrogen bromide that phenyl ether and liquid bromine or bromine generation bromination reaction generate no longer participates in bromination reaction, cause the utilization ratio of bromine atoms of liquid bromine or bromine not high, because costing an arm and a leg of liquid bromine or bromine, thereby it is this direct bromination phenyl ether preparation is higher to the technology cost of bromophenyl ether, and seriously polluted.
Summary of the invention
The purpose of this invention is to provide a kind of bromine atoms utilization ratio is higher, preparation cost is lower preparation method to bromophenyl ether.
Total technical conceive of realizing the object of the invention is: with phenyl ether and liquid bromine or bromine (being industrial liquid bromine) bromination reaction takes place directly and prepare and mainly generate bromophenyl ether and hydrogen bromide when main drawback to bromophenyl ether is liquid bromine or bromine generation bromination reaction, the hydrogen bromide that generates can not continue to participate in reaction again, also promptly there is bromine atoms over half to be wasted, again because the price of liquid bromine or bromine is higher, thereby make production cost according to high, the inventor has improved this production technique, by in above-mentioned bromination reaction raw material, adding suitable oxygenant and promotor, the hydrogen bromide that generates in following above-mentioned bromination reaction process of the effect of oxygenant and promotor is oxidized to the compound that can react with the phenyl ether continuation and generate bromophenyl ether, thereby effectively improved the utilization ratio of bromine atoms, also effectively reduced preparation cost simultaneously bromophenyl ether.
The technical scheme that realizes the object of the invention is to be reactant with phenyl ether and bromizating agent, and bromination reaction takes place under the effect of oxygenant and promotor and generate bromophenyl ether, the principal product of this bromination reaction is to bromophenyl ether, by product is an o-bromophenyl ether, and the mixture after bromination reaction is finished can directly carry out aftertreatment as the mixture after finishing to bromophenyl ether finished product or to bromination reaction and obtain bromophenyl ether finished product;
The general formula of described phenyl ether is:
In the general formula of phenyl ether, R is the alkyl of C1～C4, and promptly R is methyl, ethyl, propyl group or butyl, preferable methyl or ethyl; When R was propyl group or butyl, R not only can be the positive group of linear chain structure, can also be the isomery group with branched structure;
Described general formula to bromophenyl ether is:
In the general formula to bromophenyl ether, A is the alkyl of C1～C4, and promptly A is methyl, ethyl, propyl group or butyl, preferable methyl or ethyl; When A was propyl group or butyl, A not only can be the positive group of linear chain structure, can also be the isomery group with branched structure.
In the method for above-mentioned preparation to bromophenyl ether, the temperature with mixture in the reactor when bromination reaction carries out is controlled at 20 ℃～80 ℃, preferred 25 ℃～35 ℃; Described bromizating agent is liquid bromine, bromine or hydrogen bromide, when bromizating agent is hydrogen bromide, hydrogen bromide also can also add with the form of the gaseous state or the aqueous solution, the mol ratio of phenyl ether and the contained bromine atoms of bromizating agent is 1: 1～1: 1.3, preferred 1: 1～1.1, even bromizating agent is excessive a little, be beneficial to generate to bromophenyl ether; Described oxygenant is oxygen, air or hydrogen peroxide, when oxygenant is hydrogen peroxide, hydrogen peroxide also can also add with the form of the aqueous solution, because described oxygenant is all bought easily and to compare price lower with phenyl ether or bromizating agent, in industrial production, need not the consumption of oxygenant is controlled especially, as long as guarantee that its add-on is sufficient, if in order further to save cost, also can be that 1: 1～1: 3 scope is come the consumption of controlled oxidation agent according to the mol ratio of the amount of consumption that makes phenyl ether and the contained active oxygen of used oxygenant; Promotor is the aqueous solution of nitric acid, the aqueous solution of nitrate or the aqueous solution of nitrite, the preferred aqueous solution, the aqueous solution of SODIUMNITRATE, the aqueous solution of saltpetre, the aqueous solution of Sodium Nitrite or the aqueous solution of potassium nitrite that adopts nitric acid, and nitric acid, SODIUMNITRATE, saltpetre, Sodium Nitrite and the potassium nitrite weight percent concentration in the aqueous solution separately is 3%～15%.
Because the process that phenyl ether generation bromination reaction generates bromophenyl ether is an exothermal reaction process, in industrialized production, the disposable difficult control of temperature that the whole addings of bromizating agent will be made mixture in the reactor, and make that reaction is too violent, cause generating more impurity product, so described bromizating agent is preferably in long time period adds mixture in the reactor gradually, generally be preferably adding in 2～12 hours, so that improve the transformation efficiency of phenyl ether generation main reaction generation to bromophenyl ether.So above-mentioned preparation to a kind of preferred operating process of the method for bromophenyl ether is: in reactor, add liquid phenyl ether and promotor with agitator and thermometer, the temperature that under agitation makes the mixture in the reactor is 20 ℃～80 ℃, preferred 25 ℃～35 ℃; Then in 2～12 hours, in the mixture of reactor, add bromizating agent and oxygenant and phenyl ether generation bromination reaction is generated bromophenyl ether, when bromination reaction carries out, keep to stir and with reactor in the temperature of mixture be controlled at 20 ℃～80 ℃, preferred 25 ℃～35 ℃; Described bromizating agent is liquid bromine, bromine or hydrogen bromide, and the mol ratio of phenyl ether and the contained bromine atoms of bromizating agent is 1: 1～1: 1.1; Described oxygenant is oxygen, air or hydrogen peroxide, the mol ratio of the amount of the consumption of phenyl ether and the contained active oxygen of used oxygenant is 1: 1～1: 3, the meaning of the amount of the contained active oxygen of described oxygenant is when being used oxygenant air, oxygen or hydrogen peroxide feed can provide [0] in the mixture amount, and [0] is Sauerstoffatom; Specifically, 1 mole oxygen contains 2 moles of active oxygens, and 1 mole air contains 0.4 mole of active oxygen, and 1 mole hydrogen peroxide contains 1 mole of active oxygen; Described promotor is the aqueous solution of nitric acid, the aqueous solution of nitrate or the aqueous solution of nitrite, the preferred aqueous solution, the aqueous solution of SODIUMNITRATE, the aqueous solution of saltpetre, the aqueous solution of Sodium Nitrite or the aqueous solution of potassium nitrite that adopts nitric acid, and nitric acid, SODIUMNITRATE, saltpetre, Sodium Nitrite and the potassium nitrite weight percent concentration in its aqueous solution is 3%～15%, and the consumption of phenyl ether and the weight ratio of promotor are 1: 0.1～1: 1.After finishing bromination reaction, the transformation efficiency that phenyl ether generation main reaction generates bromophenyl ether can reach 96% like this, and the transformation efficiency that phenyl ether generation side reaction generates o-bromophenyl ether only has 2%～3%.
In the method for above-mentioned preparation to bromophenyl ether, thereby the aftertreatment that the mixture after bromination reaction finished carries out is it to be carried out separatory handle and mainly contained the organic phase solution of bromophenyl ether and mainly contain the aqueous phase solution of nitrate radical, and the organic phase solution that obtains after separatory is handled is as carrying out refinement treatment and obtain bromophenyl ether finished product to bromophenyl ether finished product or to the organic phase solution that obtains after the separatory processing; Promotor when preparation was to bromophenyl ether after wherein the aqueous phase solution that obtains after the separatory processing can be used as recycles.
In the method for above-mentioned preparation to bromophenyl ether, the refinement treatment that the organic phase solution that obtains after separatory handled carries out is that it is carried out processed and obtains the organic phase material, with the organic phase material that obtains as carrying out the sulfonation processing and obtain to bromophenyl ether finished product to bromophenyl ether finished product or to the organic phase material that obtains.The processed that the organic phase solution that obtains is carried out is that organic phase solution is distilled processing, generally can be heated to 110 ℃～120 ℃ to organic phase solution to steam moisture under environmental stress.
In the method for above-mentioned preparation to bromophenyl ether, the sulfonation processing that the organic phase material that obtains after the separatory processing is carried out is to make under agitation to add sulphonating agent in the organic phase material, make o-bromophenyl ether in the organic phase material and sulphonating agent generation sulfonation reaction and generate o-bromophenyl ether-4-Phenylsulfonic acid, it is 30 ℃～80 ℃ that sulfonation makes the temperature of mixture when handling, preferred 35 ℃～60 ℃, the mixture that obtains after sulfonation handled is as re-refine processing and obtaining bromophenyl ether finished product of the mixture that obtains after handling to bromophenyl ether finished product or to sulfonation.Described sulphonating agent is a chlorsulfonic acid; During bromination reaction when used phenyl ether and sulfonation reaction the weight ratio of used sulphonating agent be 100: 3～100: 5.
In the method for above-mentioned preparation to bromophenyl ether, the mixture that obtains after sulfonation handled is re-refined to handle several different methods can be arranged, wherein first kind of processing of re-refining is that it is neutralized and the separatory processing successively, perhaps wash successively with separatory and handle, perhaps neutralize successively, washing and separatory handle and mainly contained the organic phase solution of bromophenyl ether and mainly contain the aqueous phase solution of o-bromophenyl ether-4-Phenylsulfonic acid, with the organic phase solution that obtains as to bromophenyl ether finished product.Described neutralizing treatment is that under agitation the sodium hydroxide solution of solid-state yellow soda ash, solid-state sodium hydroxide, 3%～5% aqueous sodium carbonate or 10%～30% to be joined the pH value that makes mixture in the material be 5～6.It is under agitation that described washing is handled, and adds to make the mixture layering after entry mixes in mixture, promptly is divided into organic phase solution layer and aqueous phase solution layer, so that material soluble in water enters the aqueous phase solution layer in the mixture.Re-refine that to handle be first kind of organic phase solution of obtaining after handling re-refined to be carried out underpressure distillation again handle and obtain bromophenyl ether finished product for second kind.It is in vacuum distillation apparatus that described underpressure distillation is handled, and making pressure in the vacuum distillation apparatus is that material temperature is that 110 ℃～120 ℃ and cat head material temperature are to distill under 100 ℃～110 ℃ to obtain bromophenyl ether finished product in 10mmHg～60mmHg, the reboiler.The third is re-refined and handles is that the mixture that obtains after directly sulfonation being handled carries out rectification under vacuum and handles and obtain bromophenyl ether finished product.It is in having the rectification under vacuum device of 5～10 theoretical plate numbers that described rectification under vacuum is handled, and making pressure in the rectification under vacuum device is that material temperature is that 110 ℃～130 ℃ and cat head material temperature are 80 ℃～85 ℃ and carry out rectifying down and obtain bromophenyl ether finished product in 8mmHg～20mmHg, the reboiler.Through above-mentioned any treatment process of re-refining all can make purity be 99.9% to bromophenyl ether finished product.
In the method for above-mentioned preparation to bromophenyl ether, the mixture that after sulfonation is handled, obtains re-refine handle can obtain weight percent concentration be 99.9%～99.99% to bromophenyl ether.
The present invention has positive effect: phenyl ether that (1) is traditional and liquid bromine or bromine (being industrial liquid bromine) directly take place in the method for bromination reaction preparation to bromophenyl ether, because one of the product of bromination reaction hydrogen bromide can not react with phenyl ether again and generate the bromo phenyl ether, so having liquid bromine over half or bromine to be converted into hydrogen bromide slatterns, and the hydrogen bromide that generates also needs recycling to avoid contaminate environment, because the price of liquid bromine or bromine is comparatively expensive, cause the cost to bromophenyl ether of traditional method preparation high, the inventor has improved this production technique, by in above-mentioned bromination reaction raw material, adding suitable oxygenant and promotor, the hydrogen bromide that generates in following bromination reaction process of the effect of oxygenant and promotor is oxidized to the compound that can react with the phenyl ether continuation and generate bromophenyl ether, thereby effectively improved the utilization ratio of bromine atoms, also effectively reduced preparation cost simultaneously bromophenyl ether.(2) can mainly be contained the organic phase solution of bromophenyl ether after mixture after bromination reaction is finished among the present invention is handled through separatory and mainly contained the aqueous phase solution of nitric acid, part material when preparing the bromo phenyl ether after aqueous phase solution wherein can be used as, be that aqueous phase solution can recycle, not only reduced production cost, and there is not any disposal of pollutants, be a good green synthesis method, have the advantage of environmental protection.(3) the present invention has well solved the separation problem to bromophenyl ether and o-bromophenyl ether.Adopt distillating method to separate with o-bromophenyl ether traditionally to bromophenyl ether, because it is the two boiling point is very approaching,, extremely uneconomical so fractionation by distillation needs the distillation tower of high theoretical stage, and produces a large amount of after cut; And method of the present invention adopts sulfonation method to separate bromophenyl ether and o-bromophenyl ether, in specific temperature range, sulphonating agent such as chlorsulfonic acid react hardly with to bromophenyl ether, and generate easily and alkali reaction and o-bromophenyl ether-4-Phenylsulfonic acid soluble in water with o-bromophenyl ether, thereby conventional separation methods such as employing neutralization again, washing just the two separation reach the purpose of purification to bromophenyl ether.Separation of the present invention is to the method easy handling of bromophenyl ether and o-bromophenyl ether and efficiently thorough.(4) adopt method preparation of the present invention to bromophenyl ether, yield can reach 98%, and the purity of producing to bromophenyl ether finished product can reach 99.9% even more.
Embodiment
(embodiment 1)
The preparation process of present embodiment for carrying out in the laboratory, to the electronic agitator of 1000 milliliters be with, thermometer, the balance funnel, add 500 gram liquid phenenyl methyl ethers in the glass reaction bottle that communicates with atmosphere of inlet pipe and reflux exchanger, start agitator, then in reaction flask, add the 50g mass concentration and be rare nitric acid of 5% as promotor, utilize that material temperature is 25 ± 5 ℃ in the water-bath control reaction flask, then in reaction flask, add the liquid bromine as bromizating agent by the balance funnel, simultaneously by aerating oxygen in the material of inlet pipe in reaction flask as oxygenant, the feeding speed of oxygen will make to be had small bubbles slowly to overflow get final product in the material in the reaction flask, escaping gas drains in the water absorption cell after by reflux exchanger and is disposed in the atmosphere again after the water absorption in the reaction flask; In 10 hours, in reaction flask, at the uniform velocity add 400g liquid bromine, after the liquid bromine all adds reaction flask, continuation aerating oxygen 20 minutes in the reaction flask material, still utilize simultaneously in the water-bath control reaction flask material temperature be 25 ± 5 ℃ to finish bromination reaction, the quality that bromination reaction is finished the mixture in the post-reactor is 1020 grams, detect with vapor-phase chromatography material sampling in the reaction flask and learn this moment: the mass content of para-bromoanisole is 97.2%, and the mass content of o-bromo-anisole is 2.5%.But the mixture root that obtains behind this bromination reaction is directly as to bromophenyl ether sale of finished goods, also can continue to handle to be re-used as sale of finished goods behind the wherein contained impurity of further removal to it.The water that being used in the present embodiment in the absorption cell absorbs the micro-material of being taken out of by the oxygen of overflowing can collect after reaction finishes, and when next time, preparation was to the bromo methyl-phenoxide raw material---the water during as preparation nitric acid, can prevent contaminate environment like this.
Then the mixture that obtains behind the bromination reaction is carried out aftertreatment, be about to mixture behind the bromination reaction and add and in the separating funnel it is carried out separatory and handle, mainly contained the organic phase solution of bromophenyl ether and mainly contain the aqueous phase solution of nitrate radical; Detect with vapor-phase chromatography this organic phase solution sampling and learn this moment: the mass content of para-bromoanisole is 97.2%, and the mass content of o-bromo-anisole is 2.5%; This organic phase solution can be directly as to bromophenyl ether sale of finished goods, also can continue to handle to be re-used as sale of finished goods behind the wherein contained impurity of further removal to it.The raw material of the aqueous phase solution that obtains after separatory is handled during as preparation promotor later on---water to be recycling, and prevents contaminate environment.
The organic phase solution that obtains after then separatory being handled carries out refinement treatment, promptly it is carried out processed to improve the content of para-bromoanisole, simultaneously the set-up procedure of also handling as follow-up sulfonation; Because sulphonating agent is soluble in water and no longer valid, directly organic phase solution is carried out sulfonation if organic phase solution is not carried out processed and handle, will increase the consumption of sulphonating agent greatly.The operating process of concrete processed is under environmental stress organic phase solution to be heated to 115 ℃ to steam moisture; At this moment the organic phase material sampling after the process processed is detected with vapor-phase chromatography and learn: the mass content of para-bromoanisole is 97.2%, and the mass content of o-bromo-anisole is 2.5%; This organic phase material can be directly as to bromophenyl ether sale of finished goods, also can continue to handle to be re-used as sale of finished goods behind the wherein contained impurity of further removal to it.
Then the organic phase material that obtains after the processed being carried out sulfonation handles to remove the o-bromo-anisole in the organic phase material.The concrete operating process of carrying out the sulfonation processing is under agitation to add 20 gram chlorsulfonic acids as sulphonating agent in the organic phase material, with water-bath material temperature is controlled at 35 ± 5 ℃ simultaneously, makes o-bromophenyl ether in the organic phase material and sulphonating agent generation sulfonation reaction and generate o-bromo-anisole-4-Phenylsulfonic acid; Sampling detects with vapor-phase chromatography and learns to the mixture after oversulfonate is handled: the mass content of para-bromoanisole is 99.7%; The mixture that obtains after sulfonation is handled can be directly as to bromophenyl ether sale of finished goods, also can continue processing and be re-used as sale of finished goods after with the wherein contained impurity of further removal it.Related data sees Table 1 in the present embodiment.
(embodiment 2 to embodiment 5)
All the other are substantially the same manner as Example 1 for each embodiment among the embodiment 2 to embodiment 5, and difference is: each embodiment is raw materials used and consumption is slightly different, and this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 1.
Table 1
(embodiment 6 to embodiment 10)
All the other are substantially the same manner as Example 1 for each embodiment among the embodiment 6 to embodiment 10, and difference is: each embodiment is raw materials used and consumption is slightly different, and this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 2.
Table 2
(embodiment 11 to embodiment 15)
All the other are substantially the same manner as Example 1 for each embodiment among the embodiment 11 to embodiment 15, and difference is: each embodiment is raw materials used and consumption is slightly different, and this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 3.
Table 3
(embodiment 16)
In the present embodiment processing of re-refining that mixture neutralizes successively, separatory is handled that obtains after sulfonation is handled, to remove the o-bromo-anisole-4-Phenylsulfonic acid in the mixture that obtains after sulfonation is handled.Get the mixture that after sulfonation is handled, obtains among the embodiment 1, to its neutralize successively, the processing of re-refining of separatory, concrete working method is the aqueous sodium hydroxide solution that adds 200 grams 10% in mixture, make o-bromo-anisole-4-Phenylsulfonic acid and sodium hydroxide reaction in the organic phase material generate o-bromo-anisole-4-benzene sulfonic acid sodium salt soluble in water, when the pH of mixture value is 6, mixture is added separating funnel rock the back and carry out separatory behind the standing demix and handle and obtain organic phase solution and aqueous phase solution; The organic phase solution sampling that neutralizes successively, separatory is handled detected with vapor-phase chromatography learn: the mass content of para-bromoanisole is 99.8%; Also can repeat behind the aforesaid operations 2 to 3 times again the organic phase solution that will obtain in other embodiments directly as to bromophenyl ether sale of finished goods, also can continue processing and be re-used as sale of finished goods after with the wherein contained impurity of further removal it.Related data in the present embodiment sees Table 4.
(embodiment 17 to embodiment 20)
Each embodiment among the embodiment 17 to embodiment 20 is substantially the same manner as Example 16, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 17 to embodiment 20 is prepared among the embodiment 2 to embodiment 5, be that the mixture that obtains after sulfonation is handled that embodiment 17 is got is preparation among the embodiment 2, and the like, the mixture of being got until embodiment 20 that obtains after sulfonation is handled is preparation among the embodiment 5.Related data among embodiment 17 to embodiment 20 each embodiment sees Table 4.
Table 4
(embodiment 21)
Present embodiment is that the mixture that obtains after sulfonation is handled is washed successively, the processing of re-refining of separatory, to remove the o-bromo-anisole-4-Phenylsulfonic acid in the mixture that obtains after sulfonation is handled.Get the mixture that after sulfonation is handled, obtains among the embodiment 6, to its wash successively, the processing of re-refining of separatory, concrete working method is to add 150 gram water in mixture, make the o-bromo-anisole-4-Phenylsulfonic acid in the organic phase material soluble in water, rock the back standing demix and obtain organic phase solution and aqueous phase solution to carry out separatory to handle; The organic phase solution sampling that neutralizes successively, separatory obtains after handling detected with vapor-phase chromatography learn: the mass content of para-bromoanisole is 99.5%; Also can repeat behind the aforesaid operations 2 to 3 times again the organic phase solution that will obtain in other embodiments directly as to bromophenyl ether sale of finished goods, also can continue processing and be re-used as sale of finished goods after with the wherein contained impurity of further removal it.Related data in the present embodiment sees Table 5.
(embodiment 22 to embodiment 25)
Embodiment 22 to embodiment 25 is substantially the same manner as Example 21, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 22 to embodiment 25 is prepared among the embodiment 7 to embodiment 10, be that the mixture that obtains after sulfonation is handled that embodiment 22 is got is preparation among the embodiment 7, and the like, the mixture of being got until embodiment 25 that obtains after sulfonation is handled is preparation among the embodiment 10; Related data among the embodiment 22 to embodiment 25 among each embodiment sees Table 5.
Table 5
(embodiment 26)
Present embodiment is that the mixture that obtains after sulfonation is handled neutralizes successively, processings of re-refining of washing, separatory, to remove the o-bromo-anisole-4-Phenylsulfonic acid in the mixture that obtains after the sulfonation processing.Get the mixture that after sulfonation is handled, obtains among the embodiment 11, it is neutralized successively, washing, the processing of re-refining of separatory, concrete working method is the aqueous sodium hydroxide solution that adds 180 grams 15% in mixture, make o-bromo-anisole-4-Phenylsulfonic acid and sodium hydroxide reaction in the organic phase material generate o-bromo-anisole-4-benzene sulfonic acid sodium salt soluble in water, when the pH of mixture value is 6, mixture is moved into separating funnel, in separating funnel, add 180g water again, rock the back standing demix and then carry out the separatory processing and obtain organic phase solution and aqueous phase solution; The organic phase solution sampling that neutralizes successively, washing, separatory are handled detected with vapor-phase chromatography learn: the mass content of para-bromoanisole is 99.6%; Also can repeat behind the aforesaid operations 2 to 3 times again the organic phase solution that will obtain in other embodiments directly as to bromophenyl ether sale of finished goods, also can continue processing and be re-used as sale of finished goods after with the wherein contained impurity of further removal it.Related data in the present embodiment sees Table 6.
(embodiment 27 to embodiment 30)
Embodiment 27 to embodiment 30 is substantially the same manner as Example 26, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 27 to embodiment 30 is prepared among the embodiment 12 to embodiment 15, be that the mixture that obtains after sulfonation is handled that embodiment 27 is got is preparation among the embodiment 12, and the like, the mixture of being got until embodiment 30 that obtains after sulfonation is handled is preparation among the embodiment 15; Related data among the embodiment 27 to embodiment 30 among each embodiment sees Table 6.
Table 6
(embodiment 31)
Present embodiment is that the mixture that obtains after sulfonation is handled directly carries out the re-refining processing of rectification under vacuum and produces the para-bromoanisole finished product.Get the mixture that after sulfonation is handled, obtains among the embodiment 11, it is carried out rectification under vacuum handles, concrete working method is that organic phase solution is added in the reboiler in the rectification under vacuum device with 8 theoretical plate numbers, and making pressure in the vacuum distillation apparatus is that material temperature is that 120 ℃ and cat head material temperature are 80 ℃ and carry out rectifying down and obtain bromophenyl ether finished product in 10mmHg, the reboiler; This is detected with vapor-phase chromatography bromophenyl ether finished product sampling learn: the mass content of para-bromoanisole can reach 99.95%.Related data in the present embodiment sees Table 7.
Table 7
(embodiment 32 to embodiment 35)
Embodiment 32 to embodiment 35 and embodiment 31 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 32 to embodiment 35 is prepared among the embodiment 12 to embodiment 15, be that the mixture that obtains after sulfonation is handled that embodiment 27 is got is preparation among the embodiment 12, and the like, the mixture of being got until embodiment 35 that obtains after sulfonation is handled is preparation among the embodiment 15; Related data among the embodiment 32 to embodiment 35 among each embodiment sees Table 7.
(embodiment 36)
Present embodiment is to carrying out the underpressure distillation processing through the organic phase solution that obtains after the processing of re-refining and obtaining bromophenyl ether finished product.Repeat the foregoing description 26, get the organic phase solution after handling through neutralization, washing, separatory successively, it is carried out underpressure distillation handles, concrete working method is that organic phase solution is added in the reboiler in the vacuum distillation apparatus, making pressure in the vacuum distillation apparatus is that material temperature is that 110 ℃ and cat head material temperature are to distill under 100 ℃ to obtain bromophenyl ether finished product in 20mHg, the reboiler, and sampling detects with vapor-phase chromatography and learns to bromophenyl ether finished product to this: the mass content of para-bromoanisole can reach 99.95%.Related data in the present embodiment sees Table 8.
Table 8
(embodiment 37 to embodiment 40)
Embodiment 37 to embodiment 40 and embodiment 36 are basic identical, difference is: the organic phase solution after the process that each embodiment got among the embodiment 37 to embodiment 40 is re-refined and handled is repetition embodiment 27 to embodiment 30 and the organic phase solution that obtains, be that re-refine organic phase solution after handling of process that embodiment 37 gets is among the repetition embodiment 27 and obtain, and the like, until re-refine organic phase solution after handling of the process that embodiment 40 got is among the repetition embodiment 30 and obtain, and the related data among the embodiment 37 to embodiment 40 among each embodiment sees Table 8.
(embodiment 41)
Present embodiment is substantially the same manner as Example 1, difference is: the used phenyl ether of present embodiment is a phenyl ethyl ether, the purpose product is to the bromo phenyl ethyl ether, and other used in addition reaction masses and follow-up treating processes are also slightly different, and the detailed data among each embodiment sees Table 9.
(embodiment 42 to embodiment 45)
Each embodiment among the embodiment 42 to embodiment 45 all the other and embodiment 41 are basic identical, and difference is: each embodiment is raw materials used and consumption is slightly different, and this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 9.
Table 9
(embodiment 46 to embodiment 50)
Each embodiment among the embodiment 46 to embodiment 50 all the other and embodiment 41 are basic identical, and difference is: each embodiment is raw materials used and consumption is slightly different, and this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 10.
Table 10
(embodiment 51 to embodiment 55)
Each embodiment among the embodiment 51 to embodiment 55 all the other and embodiment 41 are basic identical, and difference is: each embodiment is raw materials used and consumption is slightly different, and this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 11.
Table 11
(embodiment 56)
Present embodiment is substantially the same manner as Example 16, and difference is: present embodiment will be removed is adjacent Bromoethyl phenyl ether-4-Phenylsulfonic acid in the mixture that sulfonation obtains after handling among the embodiment 41, and used in addition medicine and consumption are also slightly different.Related data in the present embodiment sees Table 12.
(embodiment 57 to embodiment 60)
Each embodiment and embodiment 56 among the embodiment 57 to embodiment 60 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 57 to embodiment 60 is prepared among the embodiment 42 to embodiment 45, be that the mixture that obtains after sulfonation is handled that embodiment 57 is got is preparation among the embodiment 42, and the like, the mixture of being got until embodiment 60 that obtains after sulfonation is handled is preparation among the embodiment 45.Related data among embodiment 57 to embodiment 60 each embodiment sees Table 12.
Table 12
(embodiment 61)
Present embodiment is substantially the same manner as Example 21, and difference is: present embodiment will be removed is adjacent Bromoethyl phenyl ether-4-Phenylsulfonic acid in the mixture that sulfonation obtains after handling among the embodiment 46, and used in addition medicine and consumption are also slightly different.Related data in the present embodiment sees Table 13.
(embodiment 62 to embodiment 65)
Embodiment 62 to embodiment 65 and embodiment 61 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 62 to embodiment 65 is prepared among the embodiment 47 to embodiment 50, be that the mixture that obtains after sulfonation is handled that embodiment 62 is got is preparation among the embodiment 47, and the like, the mixture of being got until embodiment 65 that obtains after sulfonation is handled is preparation among the embodiment 50; Related data among the embodiment 62 to embodiment 65 among each embodiment sees Table 13.
Table 13
(embodiment 66)
Present embodiment is substantially the same manner as Example 26, and difference is: present embodiment will be removed is adjacent Bromoethyl phenyl ether-4-Phenylsulfonic acid in the mixture that sulfonation obtains after handling among the embodiment 51, and used in addition medicine and consumption are also slightly different.Related data in the present embodiment sees Table 14.
(embodiment 67 to embodiment 70)
Embodiment 67 to embodiment 70 and embodiment 66 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 67 to embodiment 70 is prepared among the embodiment 52 to embodiment 55, be that the mixture that obtains after sulfonation is handled that embodiment 67 is got is preparation among the embodiment 52, and the like, the mixture of being got until embodiment 70 that obtains after sulfonation is handled is preparation among the embodiment 55; Related data among the embodiment 67 to embodiment 70 among each embodiment sees Table 14.
Table 14
(embodiment 71)
Present embodiment and embodiment 31 are basic identical, and difference is: present embodiment is the mixture that obtains after sulfonation is handled among the embodiment 71 directly to be carried out re-refining of rectification under vacuum handle and produce the Bromoethyl phenyl ether finished product.Related data in the present embodiment sees Table 15.
Table 15
(embodiment 72 to embodiment 75)
Embodiment 72 to embodiment 75 and embodiment 71 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 72 to embodiment 75 is prepared among the embodiment 52 to embodiment 55, be that the mixture that obtains after sulfonation is handled that embodiment 72 is got is preparation among the embodiment 52, and the like, the mixture of being got until embodiment 75 that obtains after sulfonation is handled is preparation among the embodiment 55; Related data among the embodiment 72 to embodiment 75 among each embodiment sees Table 15.
(embodiment 76)
Present embodiment is to carrying out the underpressure distillation processing through the organic phase solution that obtains after the processing of re-refining and obtaining bromophenyl ether finished product.Repeat the foregoing description 66, get the organic phase solution after handling through neutralization, washing, separatory successively, it is carried out underpressure distillation handles, concrete working method is that organic phase solution is added in the reboiler in the vacuum distillation apparatus, making pressure in the vacuum distillation apparatus is that material temperature is that 110 ℃ and cat head material temperature are to distill under 105 ℃ to obtain bromophenyl ether finished product in 30mmHg, the reboiler, and sampling detects with vapor-phase chromatography and learns to bromophenyl ether finished product to this: the mass content to Bromoethyl phenyl ether can reach 99.95%.Related data in the present embodiment sees Table 16.
Table 16
(embodiment 77 to embodiment 80)
Embodiment 77 to embodiment 80 and embodiment 76 are basic identical, difference is: the organic phase solution after the process that each embodiment got among the embodiment 77 to embodiment 80 is re-refined and handled is repetition embodiment 67 to embodiment 70 and the organic phase solution that obtains, be that re-refine organic phase solution after handling of process that embodiment 77 gets is among the repetition embodiment 67 and obtain, and the like, until re-refine organic phase solution after handling of the process that embodiment 80 got is among the repetition embodiment 70 and obtain, and the related data among the embodiment 77 to embodiment 80 among each embodiment sees Table 16.
(embodiment 81)
Present embodiment is substantially the same manner as Example 1, difference is: the used phenyl ether of present embodiment is a propyl phenyl ether, the purpose product is to the bromo propyl phenyl ether, and other used in addition reaction masses and follow-up treating processes are also slightly different, and the detailed data among each embodiment sees Table 17.
(embodiment 82 to embodiment 85)
Each embodiment among the embodiment 82 to embodiment 85 all the other and embodiment 81 are basic identical, and difference is: each embodiment is raw materials used and consumption is slightly different, and this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 17.
Table 17
(embodiment 86 to embodiment 90)
Each embodiment among the embodiment 86 to embodiment 90 all the other and embodiment 81 are basic identical, and difference is: each embodiment is raw materials used and consumption is slightly different, and this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 18.
Table 18
(embodiment 91 to embodiment 95)
Each embodiment among the embodiment 91 to embodiment 95 all the other and embodiment 81 are basic identical, and difference is: each embodiment is raw materials used and consumption is slightly different, and this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 19.
Table 19
(embodiment 96)
Present embodiment is substantially the same manner as Example 16, and difference is: present embodiment will be removed is adjacent bromobenzene propyl ether-4-Phenylsulfonic acid in the mixture that sulfonation obtains after handling among the embodiment 81, and used in addition medicine and consumption are also slightly different.Related data in the present embodiment sees Table 20.
(embodiment 97 to embodiment 100)
Each embodiment and embodiment 96 among the embodiment 97 to embodiment 100 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 97 to embodiment 100 is prepared among the embodiment 82 to embodiment 85, be that the mixture that obtains after sulfonation is handled that embodiment 97 is got is preparation among the embodiment 82, and the like, the mixture of being got until embodiment 100 that obtains after sulfonation is handled is preparation among the embodiment 85.Related data among embodiment 97 to embodiment 100 each embodiment sees Table 20.
Table 20
(embodiment 101)
Present embodiment is substantially the same manner as Example 21, and difference is: present embodiment will be removed is adjacent bromobenzene propyl ether-4-Phenylsulfonic acid in the mixture that sulfonation obtains after handling among the embodiment 86, and used in addition medicine and consumption are also slightly different.Related data in the present embodiment sees Table 21.
(embodiment 102 to embodiment 105)
Embodiment 102 to embodiment 105 and embodiment 101 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 102 to embodiment 105 is prepared among the embodiment 87 to embodiment 90, be that the mixture that obtains after sulfonation is handled that embodiment 102 is got is preparation among the embodiment 87, and the like, the mixture of being got until embodiment 105 that obtains after sulfonation is handled is preparation among the embodiment 90; Related data among the embodiment 102 to embodiment 105 among each embodiment sees Table 21.
Table 21
(embodiment 106)
Present embodiment is substantially the same manner as Example 26, and difference is: present embodiment will be removed is adjacent bromobenzene propyl ether-4-Phenylsulfonic acid in the mixture that sulfonation obtains after handling among the embodiment 91, and used in addition medicine and consumption are also slightly different.Related data in the present embodiment sees Table 22.
(embodiment 107 to embodiment 110)
Embodiment 107 to embodiment 110 and embodiment 106 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 107 to embodiment 110 is prepared among the embodiment 92 to embodiment 95, be that the mixture that obtains after sulfonation is handled that embodiment 107 is got is preparation among the embodiment 92, and the like, the mixture of being got until embodiment 110 that obtains after sulfonation is handled is preparation among the embodiment 95; Related data among the embodiment 107 to embodiment 110 among each embodiment sees Table 22.
Table 22
(embodiment 111)
Present embodiment and embodiment 31 are basic identical, and difference is: present embodiment is the mixture that obtains after sulfonation is handled among the embodiment 111 directly to be carried out re-refining of rectification under vacuum handle and produce bromobenzene propyl ether finished product.Related data in the present embodiment sees Table 23.
Table 23
(embodiment 112 to embodiment 115)
Embodiment 112 to embodiment 115 and embodiment 111 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 112 to embodiment 115 is prepared among the embodiment 92 to embodiment 95, be that the mixture that obtains after sulfonation is handled that embodiment 112 is got is preparation among the embodiment 92, and the like, the mixture of being got until embodiment 115 that obtains after sulfonation is handled is preparation among the embodiment 95; Related data among the embodiment 112 to embodiment 115 among each embodiment sees Table 23.
(embodiment 116)
Present embodiment is to carrying out the underpressure distillation processing through the organic phase solution that obtains after the processing of re-refining and obtaining bromophenyl ether finished product.Repeat the foregoing description 106, get successively through neutralization, washing, organic phase solution after separatory is handled, it is carried out underpressure distillation handles, concrete working method is that organic phase solution is added in the reboiler in the vacuum distillation apparatus, making the pressure in the vacuum distillation apparatus is 10mmHg to 30mmHg, material temperature is that 110 ℃ to 120 ℃ and cat head material temperature are to distill under 100 ℃ to 110 ℃ to obtain bromophenyl ether finished product in the reboiler, and sampling detects with vapor-phase chromatography and learns to bromophenyl ether finished product to this: the mass content to the bromobenzene propyl ether can reach 99.95%.Related data in the present embodiment sees Table 24.
Table 24
(embodiment 117 to embodiment 120)
Embodiment 117 to embodiment 120 and embodiment 116 are basic identical, difference is: the organic phase solution after the process that each embodiment got among the embodiment 117 to embodiment 120 is re-refined and handled is repetition embodiment 107 to embodiment 110 and the organic phase solution that obtains, be that re-refine organic phase solution after handling of process that embodiment 117 gets is among the repetition embodiment 107 and obtain, and the like, until re-refine organic phase solution after handling of the process that embodiment 120 got is among the repetition embodiment 110 and obtain, and the related data among the embodiment 117 to embodiment 120 among each embodiment sees Table 24.
(embodiment 121)
Present embodiment is substantially the same manner as Example 1, difference is: the used phenyl ether of present embodiment is a butoxy benzene, the purpose product is to the bromo butoxy benzene, and other used in addition reaction masses and follow-up treating processes are also slightly different, and the detailed data among each embodiment sees Table 25.
(embodiment 122 to embodiment 125)
Each embodiment among the embodiment 122 to embodiment 125 all the other and embodiment 121 are basic identical, difference is: each embodiment is raw materials used and consumption is slightly different, this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 25.
Table 25
(embodiment 126 to embodiment 130)
Each embodiment among the embodiment 126 to embodiment 130 all the other and embodiment 121 are basic identical, difference is: each embodiment is raw materials used and consumption is slightly different, this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 26.
Table 26
(embodiment 131 to embodiment 135)
Each embodiment among the embodiment 131 to embodiment 135 all the other and embodiment 121 are basic identical, difference is: each embodiment is raw materials used and consumption is slightly different, this external follow-up treating processes is also slightly different, and the detailed data among each embodiment sees Table 27.
Table 27
(embodiment 136)
Present embodiment is substantially the same manner as Example 16, and difference is: present embodiment will be removed is adjacent bromobenzene butyl ether-4-Phenylsulfonic acid in the mixture that sulfonation obtains after handling among the embodiment 121, and used in addition medicine and consumption are also slightly different.Related data in the present embodiment sees Table 28.
(embodiment 137 to embodiment 140)
Each embodiment and embodiment 136 among the embodiment 137 to embodiment 140 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 137 to embodiment 140 is prepared among the embodiment 122 to embodiment 125, be that the mixture that obtains after sulfonation is handled that embodiment 137 is got is preparation among the embodiment 122, and the like, the mixture of being got until embodiment 140 that obtains after sulfonation is handled is preparation among the embodiment 125.Related data among embodiment 137 to embodiment 140 each embodiment sees Table 28.
Table 28
(embodiment 141)
Present embodiment is substantially the same manner as Example 21, and difference is: present embodiment will be removed is adjacent bromobenzene butyl ether-4-Phenylsulfonic acid in the mixture that sulfonation obtains after handling among the embodiment 126, and used in addition medicine and consumption are also slightly different.Related data in the present embodiment sees Table 29.
(embodiment 142 to embodiment 145)
Embodiment 142 to embodiment 145 and embodiment 141 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 142 to embodiment 145 is prepared among the embodiment 127 to embodiment 130, be that the mixture that obtains after sulfonation is handled that embodiment 142 is got is preparation among the embodiment 127, and the like, the mixture of being got until embodiment 145 that obtains after sulfonation is handled is preparation among the embodiment 130; Related data among the embodiment 142 to embodiment 145 among each embodiment sees Table 29.
Table 29
(embodiment 146)
Present embodiment is substantially the same manner as Example 26, and difference is: present embodiment will be removed is adjacent bromobenzene butyl ether-4-Phenylsulfonic acid in the mixture that sulfonation obtains after handling among the embodiment 131, and used in addition medicine and consumption are also slightly different.Related data in the present embodiment sees Table 30.
(embodiment 147 to embodiment 150)
Embodiment 147 to embodiment 150 and embodiment 146 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 147 to embodiment 150 is prepared among the embodiment 132 to embodiment 135, be that the mixture that obtains after sulfonation is handled that embodiment 147 is got is preparation among the embodiment 132, and the like, the mixture of being got until embodiment 150 that obtains after sulfonation is handled is preparation among the embodiment 135; Related data among the embodiment 147 to embodiment 150 among each embodiment sees Table 30.
Table 30
(embodiment 151)
Present embodiment and embodiment 31 are basic identical, and difference is: present embodiment is the mixture that obtains after sulfonation is handled among the embodiment 151 directly to be carried out re-refining of rectification under vacuum handle and produce bromobenzene butyl ether finished product.Related data in the present embodiment sees Table 31.
Table 31
(embodiment 152 to embodiment 155)
Embodiment 152 to embodiment 155 and embodiment 151 are basic identical, difference is: the mixture that obtains after sulfonation is handled that each embodiment got among the embodiment 152 to embodiment 155 is prepared among the embodiment 132 to embodiment 135, be that the mixture that obtains after sulfonation is handled that embodiment 152 is got is preparation among the embodiment 132, and the like, the mixture of being got until embodiment 155 that obtains after sulfonation is handled is preparation among the embodiment 135; Related data among the embodiment 152 to embodiment 155 among each embodiment sees Table 31.
(embodiment 156)
Present embodiment is to carrying out the underpressure distillation processing through the organic phase solution that obtains after the processing of re-refining and obtaining bromophenyl ether finished product.Repeat the foregoing description 146, get the organic phase solution after handling through neutralization, washing, separatory successively, it is carried out underpressure distillation handles, concrete working method is that organic phase solution is added in the reboiler in the vacuum distillation apparatus, make pressure in the vacuum distillation apparatus be in 15mmHg, the reboiler material temperature be 110 and the cat head material temperature be to distill under 100 ℃ to obtain to bromophenyl ether finished product, sampling detects with vapor-phase chromatography and learns to bromophenyl ether finished product to this: the mass content to the bromobenzene butyl ether can reach 99.97%.Related data in the present embodiment sees Table 32.
Table 32
(embodiment 157 to embodiment 160)
Embodiment 157 to embodiment 160 and embodiment 156 are basic identical, difference is: the organic phase solution after the process that each embodiment got among the embodiment 157 to embodiment 160 is re-refined and handled is repetition embodiment 147 to embodiment 150 and the organic phase solution that obtains, be that re-refine organic phase solution after handling of process that embodiment 157 gets is among the repetition embodiment 147 and obtain, and the like, until re-refine organic phase solution after handling of the process that embodiment 160 got is among the repetition embodiment 150 and obtain, and the related data among the embodiment 157 to embodiment 160 among each embodiment sees Table 32.
The condition of used instrument and analysis is as follows when in the various embodiments described above sample being carried out gc analysis:
The instrument model is: the GC9790 type gas chromatograph that Wenling, Zhejiang Fu Li Analytical Instrument Co., Ltd makes; Chromatographic column model wherein is SE54,0.35 millimeter of diameter, 30 meters of length.Chromatographiccondition: 130 ℃ of column temperatures, 250 ℃ of vaporizing chambers, 250 ℃ of detectors.Detector models is flame ionization ditector FID; Sampler is a shunting; Press before the post: 0.1MPa; Sample size: 0.2 microlitre.
Obviously, the above embodiment of the present invention only is for example of the present invention clearly is described, and is not to be qualification to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give exhaustive to all embodiments.And these belong to conspicuous variation or the change that spirit of the present invention extended out and still are among protection scope of the present invention.
Claims (17)
1, a kind of preparation is to the method for bromophenyl ether, be reactant and bromination reaction takes place generate that with phenyl ether and bromizating agent the mixture after bromination reaction is finished directly carries out aftertreatment as the mixture after finishing to bromophenyl ether finished product or to bromination reaction and obtains bromophenyl ether finished product under the effect of oxygenant and promotor to bromophenyl ether; Described promotor is the aqueous solution of nitric acid, the aqueous solution of nitrate or the aqueous solution of nitrite; The general formula of described phenyl ether is:
In the general formula of phenyl ether, R is the alkyl of C1～C4; Described general formula to bromophenyl ether is:
In the general formula to bromophenyl ether, A is the alkyl of C1～C4.
2, preparation according to claim 1 is characterized in that the method for bromophenyl ether: described bromizating agent is liquid bromine, bromine or hydrogen bromide, and the mol ratio of the consumption of phenyl ether and the contained bromine atoms of bromizating agent is 1: 1～1: 1.3; Described oxygenant is oxygen, air or hydrogen peroxide; Temperature with mixture in the reactor when bromination reaction carries out is controlled at 20 ℃～80 ℃.
3, preparation according to claim 2 is characterized in that the method for bromophenyl ether: the mol ratio of the consumption of phenyl ether and the contained bromine atoms of bromizating agent is 1: 1～1: 1.1; Promotor is the aqueous solution of nitric acid, the aqueous solution of SODIUMNITRATE, the aqueous solution of saltpetre, the aqueous solution of Sodium Nitrite or the aqueous solution of potassium nitrite, and nitric acid, SODIUMNITRATE, saltpetre, Sodium Nitrite and the potassium nitrite weight percent concentration in the aqueous solution separately is 3%～15%; Temperature with mixture in the reactor when bromination reaction carries out is controlled at 25 ℃～35 ℃.
4, preparation according to claim 1 is to the method for bromophenyl ether, it is characterized in that: in reactor, add liquid phenyl ether and promotor with agitator and thermometer, the temperature that under agitation makes the mixture in the reactor is 20 ℃～80 ℃, then in mixture, add bromizating agent and oxygenant and phenyl ether generation bromination reaction generated and finish to bromophenyl ether and until bromination reaction, when bromination reaction carries out, keep stirring and with reactor in the temperature of mixture be controlled at 20 ℃～80 ℃.
5, preparation according to claim 4 is characterized in that the method for bromophenyl ether: described bromizating agent is liquid bromine, bromine or hydrogen bromide, and the mol ratio of the consumption of phenyl ether and the contained bromine atoms of bromizating agent is 1: 1～1: 1.3; Described oxygenant is oxygen, air or hydrogen peroxide; Promotor is the aqueous solution of nitric acid, the aqueous solution of nitrate or the aqueous solution of nitrite; Keep to stir when bromination reaction carries out and the temperature of mixture in the reactor is controlled at 25 ℃～35 ℃.
6, preparation according to claim 5 is characterized in that the method for bromophenyl ether: the mol ratio of the consumption of phenyl ether and the contained bromine atoms of bromizating agent is 1: 1～1: 1.1; Promotor is the aqueous solution of nitric acid, the aqueous solution of SODIUMNITRATE, the aqueous solution of saltpetre, the aqueous solution of Sodium Nitrite or the aqueous solution of potassium nitrite, and nitric acid, SODIUMNITRATE, saltpetre, Sodium Nitrite and the potassium nitrite weight percent concentration in the aqueous solution separately is 3%～15%, and the weight ratio of the consumption of phenyl ether and the consumption of promotor is 1: 0.1～1: 1; The mol ratio of the consumption of phenyl ether and the contained active oxygen of used oxygenant is 1: 1～1: 3.
7, preparation according to claim 1 is to the method for bromophenyl ether, it is characterized in that: thus the aftertreatment that the mixture after bromination reaction finished carries out is it to be carried out separatory handle and mainly contained the organic phase solution of bromophenyl ether and mainly contain the aqueous phase solution of nitrate radical, and the organic phase solution that obtains after separatory is handled is as carrying out refinement treatment and obtain bromophenyl ether finished product to bromophenyl ether finished product or to the organic phase solution that obtains after the separatory processing.
8, preparation according to claim 7 is to the method for bromophenyl ether, it is characterized in that: the refinement treatment that the organic phase solution that obtains after separatory is handled carries out is that it is carried out processed and obtains the organic phase material, with the organic phase material that obtains as carrying out the sulfonation processing and obtain to bromophenyl ether finished product to bromophenyl ether finished product or to the organic phase material that obtains.
9, preparation according to claim 8 is characterized in that the method for bromophenyl ether: the processed that the organic phase solution that obtains is carried out is that organic phase solution is distilled processing; The sulfonation processing that the organic phase material that obtains is carried out is under agitation to add sulphonating agent in the organic phase material, make o-bromophenyl ether in the organic phase material and sulphonating agent generation sulfonation reaction and generate o-bromophenyl ether-4-Phenylsulfonic acid, it is 30 ℃～80 ℃ that sulfonation makes the temperature of mixture when handling, and the mixture that obtains after sulfonation is handled is re-refined processing as the mixture that obtains after handling to bromophenyl ether finished product or to sulfonation and obtained bromophenyl ether finished product.
10, preparation according to claim 9 is characterized in that the method for bromophenyl ether: it is 35 ℃～60 ℃ that the organic phase material that obtains is carried out making the temperature of mixture when sulfonation is handled; Described sulphonating agent is a chlorsulfonic acid; The weight ratio of used sulphonating agent was 100: 3～100: 5 when used phenyl ether and sulfonation were handled during bromination reaction.
11, preparation according to claim 10 is to the method for bromophenyl ether, it is characterized in that: the mixture that obtains after sulfonation is handled is re-refined and handled is that it is neutralized and the separatory processing successively, perhaps wash successively with separatory and handle, perhaps neutralize successively, washing and separatory are handled and are mainly contained the organic phase solution of bromophenyl ether and mainly contain the aqueous phase solution of o-bromophenyl ether-4-Phenylsulfonic acid, with the organic phase solution that obtains as carrying out the underpressure distillation processing and obtain to bromophenyl ether finished product to bromophenyl ether finished product or to the re-refine organic phase solution that obtains after the processing of process.
12, preparation according to claim 11 is to the method for bromophenyl ether, it is characterized in that: it is in vacuum distillation apparatus that underpressure distillation is handled, and making pressure in the vacuum distillation apparatus is that material temperature is that 110 ℃～120 ℃ and cat head material temperature are to distill under 100 ℃～110 ℃ to obtain bromophenyl ether finished product in 10mmHg～60mmHg, the reboiler.
13, preparation according to claim 12 is to the method for bromophenyl ether, it is characterized in that: the mixture that obtains after sulfonation is handled is re-refined and handled is that it is neutralized and separatory is handled successively, and described neutralizing treatment is that under agitation solid-state yellow soda ash or solid-state sodium hydroxide to be joined the pH value that makes material in the material be 5～6.
14, preparation according to claim 12 is to the method for bromophenyl ether, it is characterized in that: the mixture that obtains after sulfonation is handled re-refine handle be to its neutralize successively, washing and separatory handle, described neutralizing treatment is that under agitation the aqueous sodium hydroxide solution of solid-state yellow soda ash, solid-state sodium hydroxide, 3%～5% aqueous sodium carbonate or 10%～30% to be joined the pH value that makes material in the material be 5～6.
15, preparation according to claim 10 is characterized in that the method for bromophenyl ether: the mixture that obtains after sulfonation is handled is re-refined and handled is it to be carried out rectification under vacuum handle and obtain bromophenyl ether finished product;
16, preparation according to claim 15 is to the method for bromophenyl ether, it is characterized in that: it is in having the rectification under vacuum device of 5～10 theoretical plate numbers that rectification under vacuum is handled, and making pressure in the rectification under vacuum device is that material temperature is that 110 ℃～130 ℃ and cat head material temperature are 80 ℃～85 ℃ and carry out rectifying down and obtain bromophenyl ether finished product in 8mmHg～20mmHg, the reboiler.
17, preparation according to claim 1 is characterized in that the method for bromophenyl ether: wherein R is methyl or ethyl; A is methyl or ethyl.
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