CN102241562A - Preparation method of symmetrical aryl iodide onium hydrochloride - Google Patents
Preparation method of symmetrical aryl iodide onium hydrochloride Download PDFInfo
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- CN102241562A CN102241562A CN2011101291956A CN201110129195A CN102241562A CN 102241562 A CN102241562 A CN 102241562A CN 2011101291956 A CN2011101291956 A CN 2011101291956A CN 201110129195 A CN201110129195 A CN 201110129195A CN 102241562 A CN102241562 A CN 102241562A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract 6
- 150000001503 aryl iodides Chemical class 0.000 title description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000001230 potassium iodate Substances 0.000 claims abstract description 18
- 235000006666 potassium iodate Nutrition 0.000 claims abstract description 18
- 229940093930 potassium iodate Drugs 0.000 claims abstract description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims abstract 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 14
- -1 aryl iodonium hydrochloride Chemical compound 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000012955 diaryliodonium Substances 0.000 claims 4
- 125000005520 diaryliodonium group Chemical group 0.000 claims 1
- PQLLEAYSRJFMFF-UHFFFAOYSA-N sulfuric acid;hydroiodide Chemical compound I.OS(O)(=O)=O PQLLEAYSRJFMFF-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 4
- RUKCJUBTRDGPCC-UHFFFAOYSA-N acetic acid;acetyl acetate Chemical compound CC(O)=O.CC(=O)OC(C)=O RUKCJUBTRDGPCC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000007812 deficiency Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- AJKLKFPOECCSOO-UHFFFAOYSA-N hydrochloride;hydroiodide Chemical compound Cl.I AJKLKFPOECCSOO-UHFFFAOYSA-N 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 25
- 229910052740 iodine Inorganic materials 0.000 description 19
- 239000011630 iodine Substances 0.000 description 19
- 239000003921 oil Substances 0.000 description 19
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 17
- 238000000605 extraction Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- DMHZUJHMYXPMHZ-UHFFFAOYSA-N C(C)(C)(C)IC1=CC=CC=C1 Chemical compound C(C)(C)(C)IC1=CC=CC=C1 DMHZUJHMYXPMHZ-UHFFFAOYSA-N 0.000 description 3
- SWUBXGOPNPAKIZ-UHFFFAOYSA-N C1(=CC=CC=C1)ICCCCCCCCCCCC Chemical compound C1(=CC=CC=C1)ICCCCCCCCCCCC SWUBXGOPNPAKIZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910018286 SbF 6 Inorganic materials 0.000 description 3
- VRGOGZVVYICPLH-UHFFFAOYSA-N iodobenzene;hydrochloride Chemical compound Cl.IC1=CC=CC=C1 VRGOGZVVYICPLH-UHFFFAOYSA-N 0.000 description 3
- 229910017008 AsF 6 Inorganic materials 0.000 description 2
- 0 CC*C(CCS)[N+](C)[O-] Chemical compound CC*C(CCS)[N+](C)[O-] 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WGINUBKWLUSQGI-UHFFFAOYSA-N C1(=CC=CC=C1)C1=CC=CC=C1.[I] Chemical compound C1(=CC=CC=C1)C1=CC=CC=C1.[I] WGINUBKWLUSQGI-UHFFFAOYSA-N 0.000 description 1
- 239000004348 Glyceryl diacetate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 235000019443 glyceryl diacetate Nutrition 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- ZPDQJYIMWOBNDH-UHFFFAOYSA-N iodo acetate Chemical compound CC(=O)OI ZPDQJYIMWOBNDH-UHFFFAOYSA-N 0.000 description 1
- JYJVVHFRSFVEJM-UHFFFAOYSA-N iodosobenzene Chemical compound O=IC1=CC=CC=C1 JYJVVHFRSFVEJM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000013526 supercooled liquid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明对称性芳基碘鎓盐酸盐的制备方法，涉及有机合成领域。以芳烃（苯、甲苯，叔丁基苯，十二烷基苯等）为原料，醋酐或醋酸或其和混合物作溶剂，与碘酸钾在浓硫酸存在下反应生成相应的芳基碘鎓硫酸氢盐，然后在氯化钠水溶液中行离子交换得到对称性芳基碘鎓盐酸盐。为了克服现有技术的不足，本发明提供了高收率、便于实现工业化生产的方法。在实验反应阶段，先将碘酸钾、醋酐（醋酸）投入反应瓶中，缓慢滴加浓硫酸后，然后再滴加芳烃，进行反应。在反应结束制备碘鎓盐酸盐时，使用萃取剂萃取反应液，去除未反应的原料或其他脂溶性好的副产物，分出下层的水层与氯化钠水溶液进行离子交换，可直接得到对称性芳基碘鎓盐酸盐产品，收率高。The invention relates to a preparation method of symmetrical aryliodonium hydrochloride, which relates to the field of organic synthesis. Aromatic hydrocarbons (benzene, toluene, tert-butylbenzene, dodecylbenzene, etc.) Hydrogen sulfate, and then perform ion exchange in aqueous sodium chloride solution to obtain symmetrical aryliodonium hydrochloride. In order to overcome the deficiencies of the prior art, the invention provides a method with high yield and convenient realization of industrialized production. In the experimental reaction stage, first put potassium iodate and acetic anhydride (acetic acid) into the reaction flask, slowly add concentrated sulfuric acid dropwise, and then add aromatic hydrocarbon dropwise to carry out the reaction. When the reaction is finished to prepare iodonium hydrochloride, the reaction solution is extracted with an extractant to remove unreacted raw materials or other by-products with good fat solubility, and the lower water layer is separated from the aqueous sodium chloride solution for ion exchange, which can be directly obtained Symmetrical aryliodonium hydrochloride product with high yield.
Description
Technical field
The present invention relates to the organic synthesis field, relate in particular to the preparation method of several symmetry aryl salt hydrochlorates.
Background technology
Because salt compounded of iodine is insoluble to non-polar solvent, to such an extent as to it must come dissolved monomer with polar solvent as the photopolymerization system of light trigger, as methyl alcohol, chloroform etc.Again because of its negative ion (AsF
6 -, SbF
6 -Deng) poisonous, so limited its application to a great extent.At these problems, synthesized novel salt compounded of iodine in recent years, mainly be in order to improve the solvability in the less solvent of polarity and to reduce toxicity.The deliquescent mode of the raising of Ti Chuing mainly contained in recent years:
(1) on phenyl ring, introduce long alkyl chain or alkoxyl group side chain, as:
The introducing of long aliphatic chain its solubleness in numerous organic solvents is increased, even good solvability is all arranged in nonpolar varsol, and raw material is cheap and easy to get, and cost is lower.Resulting salt compounded of iodine is some mixture of isomers, and then product becomes supercooled liquid, more difficult crystallization or solidify, thereby dispersed fairly good in curing formula.Research finds that also the introducing of long-chain alkoxy base not only can improve the solubleness of salt compounded of iodine, also can make its λ
MaxTo red shift, and also decrease to some degree of toxicity.This two classes salt compounded of iodine has been widely used in photocuring system.
Similar salt compounded of iodine newly developed also has:
(2) salt compounded of iodine is incorporated in the polymer chain, can be main chain, also can be side group
Toxicity is mainly derived from negative ion AsF
6 -And SbF
6 -, use BF
4 -And PF
6 -Make negative ion,,, reduced polymerization efficiency to a certain extent because of its nucleophilicity is better than the former though can avoid toxicity.And with [B (C
6H
5)
4 -] solved the problems referred to above to a great extent as the successful exploitation of the diaryl group iodized salt of negative ion.Make negative ion with it, not only nontoxic, and specific activity SbF
6 -Also strong.For example, be used to cause the silicon oxidation alkane polymerization of functionalization, its curing speed can reach 457m/min, therefore [B (C
6H
5)
4-] replacement SbF arranged greatly
6 -Trend.
General diaryl group iodized salt cation light initiator absorbs very weak more than 300nm, the conjugated degree by increasing aryl iodide compound self or introduce chromophore and can enlarge absorption region, tangible example as:
Its λ
MaxTo 265nm, corresponding ε is also from 17800mol from the 225nm red shift of phenylbenzene iodine compound
-1Lcm
-1Increase to 55000 mol
-1Lcm
-1But their solubility property is undesirable.
According to related data, the synthetic method of diaryl group iodized salt mainly contains following several:
A, aromatic compound react at sulfuric acid neutralisation of sulphuric acid idous,
B, aromatic compound react with Potassium Iodate in the vitriol oil, acetate, solution of acetic anhydride
The diacetin of D, iodosobenzene, iodobenzene or oxyiodide and other aromatic compound react under acidic conditions
The common ground of above several method can be understood as in some sense, contains the oxidation of iodine compound, cooling and aromatic compound reaction then:
In this several frequently seen synthetic report, all about 30%, raw material availability is lower for final product yield, and the present invention is doing very quantum jump aspect the raising product yield.
Summary of the invention:
Main route of the present invention is, with aromatic hydrocarbons (benzene, toluene, tert.-butylbenzene, dodecylbenzene etc.) be raw material, aceticanhydride or acetic acid or itself and mixture as solvent, react the corresponding aryl iodide hydrosulfate of generation with Potassium Iodate in the presence of the vitriol oil, row ion-exchange obtains symmetry aryl salt hydrochlorate in sodium chloride aqueous solution then.
The preparation method of the present invention's title property aryl salt hydrochlorate, its reaction equation is as follows:
（1）
（2）
The preparation method of the present invention's title property aryl salt hydrochlorate, carry out according to following step:
(1) to the preparation of diaryl iodine hydrosulfate:
Get a certain amount of Potassium Iodate, organic acid solvent, wherein the mol ratio of aromatic hydrocarbons, Potassium Iodate and the vitriol oil is 2.0:1.0:2.0, in cryosel is bathed, temperature is controlled at below 0 ℃, slowly drip the vitriol oil when stirring, the vitriol oil drips aromatic hydrocarbons after dripping and finishing, reaction 24h.Reaction finishes, and reaction system is cooled to about-5 ℃, and slowly drips proper amount of deionized water in solution.This moment, reaction solution organic solvent extraction several times divided water-yielding stratum, and with the organic solvent layer washing, combining water layer promptly obtains the aqueous solution to the iodine hydrosulfate of diaryl again.
(2) to the preparation of diaryl group iodized salt hydrochlorate:
It is soluble in water to get a certain amount of sodium-chlor, pours into above-mentionedly to carry out ion-exchange in 15 minutes to stirring in the aqueous solution of diaryl iodine hydrosulfate.Wherein sodium-chlor is 2.0:1.0 with the mol ratio of the used Potassium Iodate of reaction.Through suction filtration, obtain white to the diaryl group iodized salt hydrochlorate.
The wherein aceticanhydride of the organic acid solvent described in the step (1) or acetic acid or itself and mixture; And the mass percent of acetic acid is 25% in the solvent; Described organic solvent is benzene, toluene, sherwood oil or hexanaphthene.
Wherein the aromatic hydrocarbons described in the step (1) is
, n=1 ~ 18; Preferred benzene, toluene, tert.-butylbenzene or dodecylbenzene etc.
Advantage of the present invention: in order to overcome the deficiencies in the prior art, the invention provides high yield, be convenient to realize the method for suitability for industrialized production.
Concrete improvement is as follows:
1, in the experiment step of reaction, earlier Potassium Iodate, aceticanhydride (acetic acid) are dropped in the reaction flask, slowly drip the vitriol oil after, and then drip aromatic hydrocarbons, react.
2, when reaction finishes preparation salt compounded of iodine hydrochlorate, use extraction agent extractive reaction liquid, remove unreacted raw material or other fat-soluble good by products, water layer and the sodium chloride aqueous solution of telling lower floor carry out ion-exchange, can directly obtain symmetry aryl salt hydrochlorate product, the yield height.
Embodiment:
Embodiment 1, to the preparation of phenyl-iodide hydrochloride
The first step is to the preparation of phenyl-iodide hydrosulfate
Get Potassium Iodate 15.0g, aceticanhydride 30.0g, acetic acid 10.0g places reaction flask, cryosel is bathed hierarchy of control temperature at-5 ℃ ~-10 ℃, slowly drip the 14.0g vitriol oil in the whipping process, treat that the vitriol oil drips off after, get 11.0g benzene and slowly drip reaction system with constant pressure funnel.Continue behind the stirring reaction 24h slowly Dropwise 5 0mL deionized water, with benzene extraction 2 ~ 3 times, divide water-yielding stratum with solution, and the washing of combined benzene layer once, water layer is merged the aqueous solution that promptly obtains the phenyl-iodide hydrosulfate.
Second step is to the preparation of phenyl-iodide hydrochloride
It is soluble in water to get 8.2g sodium-chlor, slowly pours into above-mentionedly in the phenyl-iodide hydrosulfate aqueous solution, stirs, and has solid to separate out.Through suction filtration, drying, weighing obtains 9.6g white to phenyl-iodide hydrochloride solid, yield 43.4%.
As described in the first step, select different extraction agents for use, the villaumite yield that finally obtains sees the following form:
The reaction result of the different extraction agents of table 1
| Experiment | Extraction agent | Benzene: Potassium Iodate (mol ratio) | Yield (%) |
| Experiment 1 | Toluene | 2:1 | 40.1 |
| Experiment 2 | Benzene | 2:1 | 43.4 |
| Experiment 3 | Hexanaphthene | 2:1 | 34.6 |
| Experiment 4 | Sherwood oil | 2:1 | 32.1 |
| Experiment 5 | Methylene dichloride | 2:1 | 20.4 |
Embodiment 2:4,4 '-dimethyl diphenyl salt compounded of iodine hydrochlorate synthetic
The first step, 4, the preparation of 4 '-dimethyl diphenyl iodine hydrosulfate
Get Potassium Iodate 15.0g, aceticanhydride 30.0g, acetic acid 10.0g places reaction flask, cryosel is bathed hierarchy of control temperature at-5 ℃ ~-10 ℃, slowly drip the 14.0g vitriol oil in the whipping process, treat that the vitriol oil drips off after, get 13.0g toluene and slowly drip reaction system with constant pressure funnel.Slow Dropwise 5 0mL deionized water behind the continuation stirring reaction 24h with toluene extraction 2 ~ 3 times, divides water-yielding stratum with solution, and the washing of combining methylbenzene layer once, and the water layer merging is promptly obtained 4, the aqueous solution of 4 '-dimethyl diphenyl iodine hydrosulfate.
Second step, 4, the preparation of 4 '-dimethyl diphenyl salt compounded of iodine hydrochlorate
It is soluble in water to get 8.2g sodium-chlor, slowly pours into above-mentionedly 4, in 4 '-dimethyl diphenyl iodine hydrosulfate aqueous solution, stirs, and has solid to separate out.Through suction filtration, drying, weighing obtains 4 of 14.6g white, 4 '-dimethyl diphenyl salt compounded of iodine hydrochlorate, yield 60.6%.
As described in the first step, select different extraction agents for use, the villaumite yield that finally obtains sees the following form:
| Experiment | Extraction agent | Toluene: Potassium Iodate (mol ratio) | Yield (%) |
| Experiment 1 | Benzene | 2:1 | 61.10 |
| Experiment 2 | Toluene | 2:1 | 60.6 |
| Experiment 3 | Hexanaphthene | 2:1 | 40.8 |
| Experiment 4 | Sherwood oil | 2:1 | 38.3 |
| Experiment 5 | Methylene dichloride | 2:1 | 36.5 |
Embodiment 3: to the preparation of tert-butyl-phenyl salt compounded of iodine hydrochlorate
The first step is to the preparation of tert-butyl-phenyl iodine hydrosulfate
Get Potassium Iodate 15.0g, aceticanhydride 30.0g, acetic acid 10.0g places reaction flask, cryosel is bathed hierarchy of control temperature at-5 ℃ ~-10 ℃, slowly drip the 14.0g vitriol oil in the whipping process, treat that the vitriol oil drips off after, get the 18.8g tert.-butylbenzene and slowly drip reaction system with constant pressure funnel.Continue behind the stirring reaction 24h slowly Dropwise 5 0mL deionized water, with benzene extraction 2 ~ 3 times, divide water-yielding stratum with solution, and the washing of combined benzene layer once, water layer is merged the aqueous solution that promptly obtains tert-butyl-phenyl iodine hydrosulfate.
Second step is to the preparation of tert-butyl-phenyl salt compounded of iodine hydrochlorate
It is soluble in water to get 8.2g sodium-chlor, slowly pours into above-mentionedly in the tert-butyl-phenyl iodine hydrosulfate aqueous solution, stirs, and has solid to separate out.Through suction filtration, drying, weigh obtain 20.6g white to tert-butyl-phenyl salt compounded of iodine hydrochlorate, yield 68.7%.
As described in the first step, select different extraction agents for use, the villaumite yield that finally obtains sees the following form:
| Experiment | Extraction agent | Toluene: Potassium Iodate (mol ratio) | Yield (%) |
| Experiment 1 | Benzene | 2:1 | 68.7 |
| Experiment 2 | Toluene | 2:1 | 53.5 |
| Experiment 3 | Hexanaphthene | 2:1 | 43.7 |
| Experiment 4 | Sherwood oil | 2:1 | 41.4 |
| Experiment 5 | Methylene dichloride | 2:1 | 37.3 |
Embodiment 4: to the preparation of dodecylphenyl salt compounded of iodine hydrochlorate
The first step is to the preparation of dodecylphenyl iodine hydrosulfate
Get Potassium Iodate 15.0g, aceticanhydride 30.0g, acetic acid 10.0g places reaction flask, cryosel is bathed hierarchy of control temperature at-5 ℃ ~-10 ℃, slowly drip the 14.0g vitriol oil in the whipping process, treat that the vitriol oil drips off after, get the 34.5g dodecylbenzene and slowly drip reaction system with constant pressure funnel.Slow Dropwise 5 0mL deionized water behind the continuation stirring reaction 24h with benzene extraction 2 ~ 3 times, divides water-yielding stratum with solution, and the washing of combined benzene layer once, the water layer merging is promptly obtained the aqueous solution of dodecylphenyl iodine hydrosulfate.
Second step is to the preparation of dodecylphenyl salt compounded of iodine hydrochlorate
It is soluble in water to get 8.2g sodium-chlor, slowly pours into above-mentionedly in the dodecylphenyl iodine hydrosulfate aqueous solution, stirs, and has solid to separate out.Through suction filtration, drying, weigh obtain 20.9g white to dodecylphenyl salt compounded of iodine hydrochlorate, yield 45.1%.
As described in the first step, select different extraction agents for use, the villaumite yield that finally obtains sees the following form:
| Experiment | Extraction agent | Toluene: Potassium Iodate (mol ratio) | Yield (%) |
| Experiment 1 | Benzene | 2:1 | 45.1 |
| Experiment 2 | Toluene | 2:1 | 39.5 |
| Experiment 3 | Hexanaphthene | 2:1 | 31.7 |
| Experiment 4 | Sherwood oil | 2:1 | 29.4 |
| Experiment 5 | Methylene dichloride | 2:1 | 30.3 |
Claims (4)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101291956A CN102241562A (en) | 2011-05-18 | 2011-05-18 | Preparation method of symmetrical aryl iodide onium hydrochloride |
Applications Claiming Priority (1)
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| US4399071A (en) * | 1982-03-12 | 1983-08-16 | General Electric Company | Method for making diaryliodonium salts |
| CN1306224A (en) * | 1999-12-21 | 2001-08-01 | 西巴特殊化学品控股有限公司 | Iodonium salt used as potential acid provider |
| CN101139247A (en) * | 2007-09-05 | 2008-03-12 | 武汉工程大学 | Synthetic method of 4,4-didodecylphenyliodonium hexafluoroantimonate |
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| US4399071A (en) * | 1982-03-12 | 1983-08-16 | General Electric Company | Method for making diaryliodonium salts |
| CN1306224A (en) * | 1999-12-21 | 2001-08-01 | 西巴特殊化学品控股有限公司 | Iodonium salt used as potential acid provider |
| CN101139247A (en) * | 2007-09-05 | 2008-03-12 | 武汉工程大学 | Synthetic method of 4,4-didodecylphenyliodonium hexafluoroantimonate |
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