Background technology
1, the 6-hexanedial (1, be a kind of chemosterilant of novel nontoxic, quick-acting wide spectrums 6-Hexanedial), can kill most of bacteriums, bacterial propagule, fungi, gemma and virus etc. quickly and efficiently, and green noresidue, harmless; Do not corrode metallic weapon, glass and plastics, be widely used in the sterilization and the sterilization of medicine equipment, food utensil, fowl corral house etc.In addition, 1, the 6-hexanedial also is used for oil production, is used for suppressing the effect of sulphate reducing bacteria, avoids the crude oil sulphur content to raise.1, the 6-hexanedial is a kind of as linking agent, has high reactivity, binding capacity is many, product is stable and to water, acid, characteristics such as resistibility that enzyme is stronger, can be used for leather processing, biological tissue and human organ bonding with repair.1, the 6-hexanedial also is a kind of leather retanning agent, and the grain side of leather after the tanning is careful, matte even, dyeing is bright-coloured, and has characteristics such as higher perspiration resistance, thermotolerance and fastness to soaping.
At present, about 1, the synthetic rarely seen bibliographical information of 6-hexanedial synthesizes 1 abroad in China, and the 6-hexanedial mainly adopts oxidation style.Different according to oxygenant, mainly be divided into: sodium periodate oxidation, iodobenzene diacetate oxidation style, hydrogen peroxide oxidation method and ozone oxidation method.Sodium periodate is that glycol prepares aldehydes or ketones compounds oxygenant commonly used, but sodium periodate is insoluble to non-polar organic solvent, and in order to solve the solubility problem of sodium periodate, it is a kind of feasible method that sodium periodate is carried on the inert support.In recent years, the research that abroad sodium periodate is loaded on the silica gel is more.With sodium periodate/silica gel is oxidation system, and methylene dichloride is a solvent, the oxidation anti-form-1, and the 2-cyclohexanediol obtains 1, and 6-hexanedial yield is 97%.Though this method reaction yield, selectivity are all better, the preparation oxidation system need use a large amount of silica gel, and preparation technology is loaded down with trivial details, and oxygenant costs an arm and a leg.(reference Efficient and facile glycol cleavage oxidation using improved silica gel-supported sodium metaperiodate [J] .Journal of Organic Chemistry; 1997,62 (8): 2622 ~ 2624).Some chemical research persons adopt transition metal or transistion metal compound to make catalyzer, sodium periodate oxidation tetrahydrobenzene preparation 1,6-hexanedial.Such as adopting RuCl
3Catalyzer, 1, in 2-ethylene dichloride-aqueous solution, the sodium periodate oxidation tetrahydrobenzene synthesizes 1,6-hexanedial, yield 70%.This method is a raw material with the tetrahydrobenzene, need not to prepare oxidation system, but the catalyzer price is more expensive and can not recycle, and reaction yield is not high.(reference Ruthenium-catalyzed oxidative cleavage of olefins to aldehydes [J] .Journal of Organic Chemistry, 2001,66 (14): 4814 ~ 4818).
Iodobenzene diacetate (PhI (OAC)
2) be a kind of gentleness, nontoxic oxygenant and have good selective oxidation property.Bibliographical information with PhI (OAC)
2Oxidation 1,2-cyclohexanediol preparation 1, the 6-hexanedial, oxidation cis and trans 1 under the room temperature, 2-cyclohexanediol gained 1,6-hexanedial yield is respectively 92% and 95%.This method reaction is simpler, easy and simple to handle, and reaction conditions is gentleness also, but oxygenant is difficult for acquisition, and it is inconvenient that product aftertreatment and separation are purified.(reference An expedient procedure for the oxidative cleavage of olefinic bonds with PhI (OAc)
2, NMO, and catalytic OsO
4[J] .Organic Letters, 2010,12 (7): 1552 ~ 1555).
Ydrogen peroxide 50 is a kind of very strong oxygenant, generates water owing to discharge active oxygen after the ydrogen peroxide 50 reaction, therefore often is called as eco-friendly cleaning oxidizer.Bibliographical information make catalyzer with the peroxide niobic acid, acetate is solvent, 50% hydrogen peroxide oxidation tetrahydrobenzene preparation 1, the 6-hexanedial, transformation efficiency 100%, but 1, the selectivity of 6-hexanedial only has 40%.(ydrogen peroxide 50 selective oxidation cyclopentenes prepares LUTARALDEHYDE [J] under the reference peroxide Niobic Acid. Fudan Journal (natural science edition), 2002,41 (3): 317 ~ 319,324).Employing contains nioium complex [∏-C
5H
4N (CH
2)
13CH
3]
2[Nb
4O
6(O
2)
2(PO
4)
2] 6H
2O is used for the oxidation of ydrogen peroxide 50 catalysis cycloolefin, and the cyclopentenes oxidation obtains the yield of LUTARALDEHYDE up to 80%, but the similarity condition cyclohexene oxide; The transformation efficiency of tetrahydrobenzene and 1, the selectivity of 6-hexanedial is all lower, in the alcohol solvent; Transformation efficiency is 52%, 1,6-hexanedial selectivity 42%.(reference A new process for preparing dialdehyde by catalytic oxidation of cyclic olefins with aqueous hydrogen peroxide [J] .Chinese Journal of Chemistry; 2000,18 (2): 252 ~ 255).This method ydrogen peroxide 50 is inexpensive cleaning oxidizer, but reaction preference is low, and 1,6-hexanedial poor stability is prone to be oxidized to acid, therefore need study the catalyzer of high reactivity and highly selective for hydrogen peroxide oxidation.
In the past few years, the application of ozone in organic synthesis is increasingly extensive, particularly the reaction of unsaturated olefin oxidation scission is had more economical, remarkable advantages more.Ozone is a kind of strong oxidizer, has advantages such as oxidation capacity is strong, selectivity is high, speed of response is fast, and can decompose voluntarily after the reaction end, can not cause environmental pollution, is the oxygenant of a kind of " totally ", is fit to the development trend of current green chemical industry.The ozone oxidation tetrahydrobenzene produces 1, the 6-hexanedial, at first under the low temperature in solution ozone oxidation alkene obtain ozonide, then it is carried out reduction decomposition and obtains 1, the 6-hexanedial.The reductive agent that reduction decomposition tetrahydrobenzene ozonide is commonly used has (CH
3)
2S, Ph
3P, Pd/H
2Bibliographical information be solvent with the methylene dichloride ,-78 ℃ of ozonize tetrahydrobenzene obtain 74% ozonide in the presence of methylpropanoic acid ketone, triphenyl phosphorus reduction obtains 1, the 6-hexanedial, this step yield is 86%.Though this method reduction decomposition yield is high, the reductive agent price is more expensive, and the product separation difficulty.(reference Syntheses of bifunctional compounds from cycloalkenes via ozonide intermediates [J] .Tetrahedron, 1997,53 (14): 5217 ~ 5232).Bibliographical information employing methyl alcohol make solvent, the ozonize tetrahydrobenzene at first obtains ozonide under-60 ℃ of low temperature, adopts dimethyl thioether to its reduction decomposition then, obtains 1,6-hexanedial yield is 62%.(reference A new and convenient method for converting olefins to aldehydes [J] .Tetrahedron Letters, 1966,36:4273 ~ 4278).US 2733270 is a catalyzer with Pd/C (containing 5% Pd), with Pd/H
2Or Zn-CH
3COOH is reductive agent preparation 1,6-hexanedial, yield 54%-59%.Though catalytic hydrogenation reduction decomposition ozonide reduction efficiency is better, the catalyzer price is more expensive, operation inconvenience.Above-mentioned zinc powder-acetate produces nascent hydrogen reduction decomposition method, and the low-temp reaction condition is harsh, and the reaction times is longer.
Summary of the invention
The object of the present invention is to provide a kind ofly 1, the preparation method of 6-hexanedial overcomes deficiency of the prior art.It is low to reach production cost, and reaction conditions is gentle, and after the reaction, product separation is easy, energy-saving and cost-reducing, thereby sets up a kind of preparation 1, the method capable of being industrialized of 6-hexanedial.
The present invention prepares 1, and the technical scheme of 6-hexanedial is following, realizes through following steps:
(1) tetrahydrobenzene, organic solvent, glacial acetic acid are added in the reaction vessel, control reaction temperature feeds O at-20 ℃ ~ 10 ℃
3/ O
2Carry out ozonization, tail gas absorbs unreacted ozone completely through liquor kalii iodide earlier, reclaims a small amount of tetrahydrobenzene of evaporable and organic solvent through glacial acetic acid again.Oxidation finishes the logical N in back
2Get rid of redundant ozone, obtain ozonization liquid; The quality percentage composition of ozone is 3% ~ 10% in said ozone and the oxygen mixed gas;
(2) ozonization liquid is directly carried out reduction decomposition: it is dropped in the aqueous solution that contains zinc powder; The stirring at room reaction filters out unreacted zinc powder completely under the nitrogen protection, and standing demix is isolated oil phase, revolve to steam to obtain 1 except that desolvating, and 6-hexanedial bullion, underpressure distillation obtains 1,6-hexanedial product.Water through concentrate, crystallization, refining anhydrous zinc acetate sub product, concentrated aqueous liquid is used for the ozonide reduction decomposition, recycles.
The said reaction vessel of step (1) is flask or blistering reaction tower, is glass material, and the low temperature reflux condensing works is equipped with at the reaction vessel top.
The said organic solvent of step (1) is methylene dichloride, chloroform, 1,2-ethylene dichloride, pimelinketone or ETHYLE ACETATE; The volume ratio that organic solvent adds volume and tetrahydrobenzene is 3 ~ 10: 1; Preferred-10 ℃ ~ 0 ℃ of the said ozonization temperature of step (1).
The mol ratio of tetrahydrobenzene, glacial acetic acid, zinc powder is 1: 1 ~ 4: 0.8 ~ 1.5, preferred 1: 1.5 ~ 2.5: 0.8 ~ 1.1.
With CDCl
3Be solvent, to 1 of preparation, 6-hexanedial product carries out
1H-NMR,
13C-NMR analyzes, and on NEXUS-470 type Fourier transform infrared spectroscopy (FT-IR) appearance, product is carried out infrared analysis; The product of preparation is with its content of GC-9800 gas Chromatographic Determination.
Chromatographic condition is following:
Chromatographic column: Φ 1 μ m (I.D.) * 30 mm capillary column look SE-30;
Carrier gas: N
2Detector: FID; Press before the post: 0.06MPa; Vaporizing chamber: 250 ℃; Detector: 250 ℃; Temperature programming: 160 ℃ of insulation 4 min, 20 ℃/min, rise to 200 ℃, reduce to 160 ℃ behind the insulation 5min.
By-product acetic acid zinc content is according to HG/T 3-1098-77 methods analyst.
Preparing method's advantage of the present invention is: 1, be oxygenant with ozone, the oxygenant activity is high, selectivity is good, cheap and easy to get.Selecting glacial acetic acid and organic solvent for use is mixed solvent; Make tetrahydrobenzene and ozonide that solvability preferably arranged; Avoided the generation of thickness ozonide; Reaction solution viscosity is low, and the dispersion effect of ozone gas in reaction solution is good, and the existence of glacial acetic acid not only makes the ozonide of generation stablize but also help the carrying out of reduction reaction.2, reaction conditions is gentle, and process is easy, and there are obvious phase interface in reacted organic phase and product (oil phase) with inorganic salt solution (water), can realize effective separation smoothly, and separating technology is easy, and is energy-saving and cost-reducing greatly.Can obtain 1 more than 97%, 6-hexanedial through further underpressure distillation.3, water inorganic salt solution (mainly being zinc acetate) through evaporation, concentrate, crystallization can obtain important by-products zinc acetate bullion, refining back purity reaches more than 98.0% the water liquid that concentrates out the reduction decomposition that is used for ozonide capable of circulation.This method has the good industrial application prospect.
Embodiment
For the present invention is better explained, it is following to lift embodiment:
Embodiment one
(1) in there-necked flask, add tetrahydrobenzene 50mmol, methylene dichloride 15mL and glacial acetic acid 6g (100mmol) put into low-temp reaction and bathe, and stir and treat that system temperature reduces to-20 ℃, feed O
3/ O
2Carry out ozonization.Tail gas absorbs unreacted ozone completely through liquor kalii iodide earlier, reclaims a small amount of tetrahydrobenzene of evaporable and organic solvent through glacial acetic acid again.With 5% Br
2/ CCl
4Solution detection reaction terminal point, oxidation finish the logical 2 min N in back
2Get rid of redundant ozone, obtain ozonization liquid, ozonide does not separate direct entering reduction reaction.
(2) ozonization liquid is moved in the constant pressure funnel, drop in the zero(ppm) water that contains activated zinc powder 50mmol, 0.5h dropwises; Stirring at room reaction 50min filters out unreacted zinc powder completely under the nitrogen protection, isolates oil phase, revolve steam remove desolvate 1,6-hexanedial bullion, 1,6-hexanedial bullion gets the finished product through underpressure distillation.Gas chromatographic analysis, 1,6-hexanedial yield 53.3%.Water through concentrate, crystallization, refining anhydrous zinc acetate sub product, concentrated aqueous liquid is used for the ozonide reduction decomposition, recycles.
Embodiment two
(1) in there-necked flask, add tetrahydrobenzene 50mmol, chloroform 25mL and glacial acetic acid 5.4g (90 mmol) put into low-temp reaction and bathe, and stir and treat that system temperature reduces to-10 ℃, feed O
3/ O
2Carry out oxidizing reaction.Tail gas absorbs unreacted ozone completely through liquor kalii iodide earlier, reclaims a small amount of tetrahydrobenzene of evaporable and organic solvent through glacial acetic acid again.With 5% Br
2/ CCl
4Solution detection reaction terminal point, oxidation finish the logical 2 min N in back
2Get rid of redundant ozone, obtain ozonization liquid, ozonide does not separate direct entering reduction reaction.
(2) ozonization liquid is moved in the constant pressure funnel, drop in the zero(ppm) water that contains activated zinc powder 45mmol, 0.5h dropwises; Stirring at room reaction 60min filters out unreacted zinc powder completely under the nitrogen protection, isolates oil phase, revolve steam remove desolvate 1,6-hexanedial bullion, 1,6-hexanedial bullion gets the finished product through underpressure distillation.Gas chromatographic analysis, 1,6-hexanedial yield 56.9%.Water through concentrate, crystallization, refining anhydrous zinc acetate sub product, concentrated aqueous liquid is used for the ozonide reduction decomposition, recycles.
Embodiment three
(1) in there-necked flask, add tetrahydrobenzene 50mmol, 1,2-ethylene dichloride 40mL and glacial acetic acid 6.6g (110 mmol) put into low-temp reaction and bathe, and stir and treat that system temperature reduces to 5 ℃, feed O
3/ O
2Carry out oxidizing reaction.Tail gas absorbs unreacted ozone completely through liquor kalii iodide earlier, reclaims a small amount of tetrahydrobenzene of evaporable and organic solvent through glacial acetic acid again.With 5% Br
2/ CCl
4Solution detection reaction terminal point, oxidation finish the logical 2 min N in back
2Get rid of redundant ozone, obtain ozonization liquid, ozonide does not separate direct entering reduction reaction.
(2) ozonization liquid is moved in the constant pressure funnel, drop in the zero(ppm) water that contains activated zinc powder 60mmol, 0.5h dropwises; Stirring at room reaction 75min filters out unreacted zinc powder completely under the nitrogen protection, isolates oil phase, revolve steam remove desolvate 1,6-hexanedial bullion, 1,6-hexanedial bullion gets the finished product through underpressure distillation.Gas chromatographic analysis, 1,6-hexanedial yield 60.2%.Water through concentrate, crystallization, refining anhydrous zinc acetate sub product, concentrated aqueous liquid is used for the ozonide reduction decomposition, recycles.
Embodiment four
(1) in there-necked flask, add tetrahydrobenzene 50mmol, 1,2-ethylene dichloride 50mL and glacial acetic acid 6g (100 mmol) put into low-temp reaction and bathe, and stir and treat that system temperature reduces to 0 ℃, feed O
3/ O
2Carry out oxidizing reaction.Tail gas absorbs unreacted ozone completely through liquor kalii iodide earlier, reclaims a small amount of tetrahydrobenzene of evaporable and organic solvent through glacial acetic acid again.With 5% Br
2/ CCl
4Solution detection reaction terminal point, oxidation finish the logical 2 min N in back
2Get rid of redundant ozone, obtain ozonization liquid, ozonide does not separate direct entering reduction reaction.
(2) ozonization liquid is moved in the constant pressure funnel, drop in the zero(ppm) water that contains activated zinc powder 55mmol, 0.5h dropwises; Stirring at room reaction 55min filters out unreacted zinc powder completely under the nitrogen protection, isolates oil phase, revolve steam remove desolvate 1,6-hexanedial bullion, 1,6-hexanedial bullion gets the finished product through underpressure distillation.Gas chromatographic analysis, 1,6-hexanedial yield 62.0%.Water through concentrate, crystallization, refining anhydrous zinc acetate sub product, concentrated aqueous liquid is used for the ozonide reduction decomposition, recycles.
Embodiment five
(1) in there-necked flask, add tetrahydrobenzene 50mmol, 1,2-ethylene dichloride 30mL and glacial acetic acid 3.6g (60 mmol) put into low-temp reaction and bathe, and stir and treat that system temperature reduces to-5 ℃, feed O
3/ O
2Carry out oxidizing reaction.Tail gas absorbs unreacted ozone completely through liquor kalii iodide earlier, reclaims a small amount of tetrahydrobenzene of evaporable and organic solvent through glacial acetic acid again.With 5% Br
2/ CCl
4Solution detection reaction terminal point, oxidation finish the logical 2 min N in back
2Get rid of redundant ozone, obtain ozonization liquid, ozonide does not separate direct entering reduction reaction.
(2) ozonization liquid is moved in the constant pressure funnel, drop in the zero(ppm) water that contains activated zinc powder 40mmol, 0.5h dropwises; Stirring at room reaction 60min filters out unreacted zinc powder completely under the nitrogen protection, isolates oil phase, revolve steam remove desolvate 1,6-hexanedial bullion, 1,6-hexanedial bullion gets the finished product through underpressure distillation.Gas chromatographic analysis, 1,6-hexanedial yield 51.1%.Water through concentrate, crystallization, refining anhydrous zinc acetate sub product, concentrated aqueous liquid is used for the ozonide reduction decomposition, recycles.
Embodiment six
(1) in there-necked flask, add tetrahydrobenzene 50mmol, 1,2-ethylene dichloride 35mL and glacial acetic acid 6g (100 mmol) put into low-temp reaction and bathe, and stir and treat that system temperature reduces to-15 ℃, feed O
3/ O
2Carry out oxidizing reaction.Tail gas absorbs unreacted ozone completely through liquor kalii iodide earlier, reclaims a small amount of tetrahydrobenzene of evaporable and organic solvent through glacial acetic acid again.With 5% Br/CCl
4Solution detection reaction terminal point, oxidation finish the logical 2 min N in back
2Get rid of redundant ozone, obtain ozonization liquid, ozonide does not separate direct entering reduction reaction.
(2) ozonization liquid is moved in the constant pressure funnel, drop in the zero(ppm) water that contains activated zinc powder 55mmol, 0.5h dropwises; Stirring at room reaction 65min filters out unreacted zinc powder completely under the nitrogen protection, isolates oil phase, revolve steam remove desolvate 1,6-hexanedial bullion, 1,6-hexanedial bullion gets the finished product through underpressure distillation.Gas chromatographic analysis, 1,6-hexanedial yield 62.6%.Water through concentrate, crystallization, refining anhydrous zinc acetate sub product, concentrated aqueous liquid is used for the ozonide reduction decomposition, recycles.
Embodiment seven
(1) in there-necked flask, add tetrahydrobenzene 50mmol, 1,2-ethylene dichloride 30mL and glacial acetic acid 9g (150 mmol) put into low-temp reaction and bathe, and stir and treat that system temperature reduces to 0 ℃, feed O
3/ O
2Carry out oxidizing reaction.Tail gas absorbs unreacted ozone completely through liquor kalii iodide earlier, reclaims a small amount of tetrahydrobenzene of evaporable and organic solvent through glacial acetic acid again.With 5% Br
2/ CCl
4Solution detection reaction terminal point, oxidation finish the logical 2 min N in back
2Get rid of redundant ozone, obtain ozonization liquid, ozonide does not separate direct entering reduction reaction.
(2) ozonization liquid is moved in the constant pressure funnel, drop in the zero(ppm) water that contains activated zinc powder 70mmol, 0.5h dropwises; Stirring at room reaction 45min filters out unreacted zinc powder completely under the nitrogen protection, isolates oil phase, revolve steam remove desolvate 1,6-hexanedial bullion, 1,6-hexanedial bullion gets the finished product through underpressure distillation.Gas chromatographic analysis, 1,6-hexanedial yield 54.4%.Water through concentrate, crystallization, refining anhydrous zinc acetate sub product, concentrated aqueous liquid is used for the ozonide reduction decomposition, recycles.
Embodiment eight
(1) in there-necked flask, add tetrahydrobenzene 50mmol, ETHYLE ACETATE 35mL and glacial acetic acid 6g (100 mmol) put into low-temp reaction and bathe, and stir and treat that system temperature reduces to-5 ℃, feed O
3/ O
2Carry out oxidizing reaction.Tail gas absorbs unreacted ozone completely through liquor kalii iodide earlier, reclaims a small amount of tetrahydrobenzene of evaporable and organic solvent through glacial acetic acid again.With 5% Br
2/ CCl
4Solution detection reaction terminal point, oxidation finish the logical 2 min N in back
2Get rid of redundant ozone, obtain ozonization liquid, ozonide does not separate direct entering reduction reaction.
(2) ozonization liquid is moved in the constant pressure funnel, drop in the zero(ppm) water that contains activated zinc powder 60mmol, 0.5h dropwises; Stirring at room reaction 80min filters out unreacted zinc powder completely under the nitrogen protection, isolates oil phase, revolve steam remove desolvate 1,6-hexanedial bullion, 1,6-hexanedial bullion gets the finished product through underpressure distillation.Gas chromatographic analysis, 1,6-hexanedial yield 45.6%.Water through concentrate, crystallization, refining anhydrous zinc acetate sub product, concentrated aqueous liquid is used for the ozonide reduction decomposition, recycles.
Embodiment nine
(1) in there-necked flask, add tetrahydrobenzene 50mmol, pimelinketone 30mL and glacial acetic acid 5.7g (95 mmol) put into low-temp reaction and bathe, and stir and treat that system temperature reduces to 10 ℃, feed O
3/ O
2Carry out oxidizing reaction.Tail gas absorbs unreacted ozone completely through liquor kalii iodide earlier, reclaims a small amount of tetrahydrobenzene of evaporable and organic solvent through glacial acetic acid again.With 5% Br
2/ CCl
4Solution detection reaction terminal point, oxidation finish the logical 2 min N in back
2Get rid of redundant ozone, obtain ozonization liquid, ozonide does not separate direct entering reduction reaction.
(2) ozonization liquid is moved in the constant pressure funnel, drop in the zero(ppm) water that contains activated zinc powder 50mmol, 0.5h dropwises; Stirring at room reaction 50min filters out unreacted zinc powder completely under the nitrogen protection, isolates oil phase, revolve steam remove desolvate 1,6-hexanedial bullion, 1,6-hexanedial bullion gets the finished product through underpressure distillation.Gas chromatographic analysis, 1,6-hexanedial yield 55.5%.Water through concentrate, crystallization, refining anhydrous zinc acetate sub product, concentrated aqueous liquid is used for the ozonide reduction decomposition, recycles.
Embodiment ten
(1) in the blistering reaction tower, add tetrahydrobenzene 0.1mol, 1,2-ethylene dichloride 60mL and glacial acetic acid 12g (200 mmol) put into low-temp reaction and bathe, and stir and treat that system temperature reduces to-5 ℃, feed O
3/ O
2Carry out oxidizing reaction.Tail gas absorbs unreacted ozone completely through liquor kalii iodide earlier, reclaims a small amount of tetrahydrobenzene of evaporable and organic solvent through glacial acetic acid again.With 5% Br
2/ CCl
4Solution detection reaction terminal point, oxidation finish the logical 2 min N in back
2Get rid of redundant ozone, obtain ozonization liquid, ozonide does not separate direct entering reduction reaction.
(2) ozonization liquid is moved in the constant pressure funnel, drop in the zero(ppm) water that contains activated zinc powder 0.11mol, 0.5h dropwises; Stirring at room reaction 90min filters out unreacted zinc powder completely under the nitrogen protection, isolates oil phase, revolve steam remove desolvate 1,6-hexanedial bullion, 1,6-hexanedial bullion gets the finished product through underpressure distillation.Gas chromatographic analysis, 1,6-hexanedial yield 60.7%.Water through concentrate, crystallization, refining anhydrous zinc acetate sub product, concentrated aqueous liquid is used for the ozonide reduction decomposition, recycles.