CN104557516A - Method for preparing 18O-crystal glyoxylic acid - Google Patents
Method for preparing 18O-crystal glyoxylic acid Download PDFInfo
- Publication number
- CN104557516A CN104557516A CN201410804848.XA CN201410804848A CN104557516A CN 104557516 A CN104557516 A CN 104557516A CN 201410804848 A CN201410804848 A CN 201410804848A CN 104557516 A CN104557516 A CN 104557516A
- Authority
- CN
- China
- Prior art keywords
- crystal
- oxoethanoic acid
- reaction
- heavy oxygen
- abundance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention relates to a method for preparing 18O-crystal glyoxylic acid. The method comprises the following steps: (1) adding common crystal glyoxylic acid into a sodium hydroxide heavy oxygen water solution for recrystallizing, thereby obtaining purified crystal glyoxylic acid; (2) adding the purified crystal glyoxylic acid and heavy oxygen water into a reaction kettle to carry out an oxygen isotope exchange reaction, thereby obtaining a 18O-crystal glyoxylic acid heavy oxygen water solution; (3) performing reduced pressure distillation, concentrating and crystallizing after the reaction is ended, thereby obtaining 18O-crystal glyoxylic acid; and (4) repeating the steps (2) and (3), thereby obtaining high-abundance 18O-crystal glyoxylic acid. Compared with the prior art, the method disclosed by the invention has the advantages that natural glyoxylic acid with the abundance of 0.204 percent is purified to carry out the oxygen isotope exchange reaction with the heavy oxygen water in the reaction kettle, and finally the 18O-glyoxylic acid product with the abundance of 1-99 percent can be obtained. The method disclosed by the invention is simple in process, easy and convenient to operate, low in energy consumption, high in product purity and low in H218O loss.
Description
Technical field
The invention belongs to technical field of fine, especially relate to one
18the preparation method of O-crystal oxoethanoic acid.
Background technology
Occurring in nature oxygen (O) unit have
16o,
17o,
18o tri-kinds of stable isotopes, total mass number is 16,17,18 respectively, and natural abundance is respectively 99.76%, 0.036%, 0.204%.
18o is as a kind of stable isotope, and main application utilizes isotopic tracer technique, is applied to organism metabolism, pharmaceutical synthesis step controls, the research of environmental science and water geology, chemical chain characteristic and the aspect such as chemical reaction mechanism, nuclear medicine diagnostic.Heavy oxygen water (H
2 18o) molecular weight 20.0, its chemical property is identical with ortho-water, is containing of comparatively common easy preservation
18the material of O.
Oxoethanoic acid (HOCCOOH) is also known as glyoxylic acid, and Oxoacetic Acid is the simplest aldehydic acid.In the molecule of oxoethanoic acid, existing carboxyl has aldehyde radical again, and its chemical property is very active, is a kind of important industrial chemicals and organic synthesis intermediate, is also widely used in the industries such as spices, essence, medicine, agricultural chemicals.Crystal-type oxoethanoic acid has three kinds of forms according to band crystal water difference: not being with crystal water oxoethanoic acid (HOCCOOH), is monoclinic crystal body, fusing point 98 DEG C; Be with half crystal water oxoethanoic acid (HOCCOOH1/2H
2o), be colourless column crystallization, fusing point is 70 ~ 75 DEG C; Be with a crystal water oxoethanoic acid (HOCCOOHH
2o), fusing point 50 ~ 52 DEG C.Crystal-type oxoethanoic acid has tedious taste, and be the acid of a kind of severe corrosive, easy deliquescence, exposes and can form pulpous state in atmosphere.
Due to the special property of oxoethanoic acid,
18the oxoethanoic acid crystal of O mark may be used for the research of the aspects such as medicine, biology, chemistry, has more wide prospect.
Summary of the invention
Object of the present invention be exactly provide to overcome defect that above-mentioned prior art exists a kind of simple, easy to operate, less energy consumption, product purity are high,
18o loses that few abundance scope is 1% ~ 99%, purity is 70% ~ 99.9%
18the preparation method of O-crystal oxoethanoic acid.
Object of the present invention can be achieved through the following technical solutions:
A kind of
18the preparation method of O-crystal oxoethanoic acid, the method comprises the following steps:
(1) common crystal oxoethanoic acid is added recrystallization in the sodium hydroxide heavy oxygen aqueous solution, obtain the crystal oxoethanoic acid after purifying;
(2) the crystal oxoethanoic acid after purifying and heavy oxygen water are put into the permutoid reaction that reactor carries out oxygen isotope; protection gas is filled in reactor; temperature of reaction controls at 20 ~ 80 DEG C; for adding fast response; stirring can be aided with; reaction times is 0.5 ~ 3 day, and the molar ratio of crystal oxoethanoic acid and heavy oxygen water controls, at 1:5 ~ 1:100, to obtain
18the O-oxoethanoic acid heavy oxygen aqueous solution; Oxygen isotope exchange reactive chemistry equation is: C
2h
2 16o
3+ H
2 18o → C
2h
2 18o
3+ H
2 16o;
(3), after reaction terminates, underpressure distillation condensing crystal, obtains
18o-crystal oxoethanoic acid, reclaims the heavy oxygen water of evaporation simultaneously;
(4) repeat step (2) and obtain more high abundance with step (3)
18o-crystal oxoethanoic acid.
Step (4) obtains
18o-crystal oxoethanoic acid abundance is 1% ~ 99%, and be preferably 50% ~ 99%, purity is 70% ~ 99.9%.
Step (4) obtains
18o-crystal oxoethanoic acid exists with the form of a water oxoethanoic acid, anhydrous oxoethanoic acid or hypocrystalline water oxoethanoic acid.
In common crystal oxoethanoic acid described in step (1)
18o is natural abundance (0.204%), and purity is 70% ~ 99.9%, exists with the form of a water oxoethanoic acid, anhydrous oxoethanoic acid or hypocrystalline water oxoethanoic acid.
The method of carrying out recrystallization in step (1) is specially:
A common crystal oxoethanoic acid, a small amount of sodium hydroxide heavy oxygen aqueous solution are put into reaction kettle for reaction by (), protection gas filled by reactor, temperature controls at 15 ~ 40 DEG C, reaction times was at 10 ~ 60 minutes, crystal oxoethanoic acid and sodium hydroxide molar ratio are 1000:(1 ~ 10), sodium hydroxide heavy oxygen aqueous solution volumetric molar concentration is 1 ~ 5mol/L;
Vacuumize underpressure distillation after (b) reaction to concentrate; temperature range is at 45 ~ 55 DEG C; pressure vacuum degree is at 20-95KPa; rapidly temperature is reduced to 5 to-5 DEG C until liquid concentration to during the 15%-60% of original solution volume; then crystallization 1-3 hour is incubated; after solid-liquid separation, get the loft drier inner drying that solids is placed with the filling of protection gas, obtain the crystal oxoethanoic acid after purifying.The principal reaction related in step (1) is oxalic dialdehyde with the neutralization reaction etc. of the disproportionation reaction of aqueous sodium hydroxide solution, hydrochloric acid and sodium hydroxide.
In heavy oxygen water described in step (2)
18the abundance scope of O is 5% ~ 99%.
In step (3), during underpressure distillation condensing crystal, temperature is 15-90 DEG C, and vacuum tightness is 20 ~ 95KPa.
Described protection gas is helium, neon, argon gas, xenon or nitrogen.
The sodium hydroxide heavy oxygen aqueous solution described in step (1) is that sodium hydrate solid is dissolved in heavy oxygen water and prepares, or is obtained by sodium Metal 99.5 and the reaction of high abundance heavy oxygen water, and the chemical equation of this reaction is 2Na+2H
2o=2NaOH+H
2.
Preparation method of the present invention has following characteristics:
1), due to
18contained by O-oxoethanoic acid
18o is easy to react with oxygen, ortho-water etc. and cause the reduction of abundance, if adopt the crystallization condition of common oxoethanoic acid, obtained
18o-oxoacetic acid product abundance can be very low, therefore, for improving
18in O-oxoacetic acid product
18the abundance of O, the present invention requires more harsh to crystallization condition, uses the heavy oxygen water of certain abundance just passable when crystallization, if want to obtain high abundance
18o-oxoethanoic acid just needs more abundant heavy oxygen water, and in reaction vessel, fills the rare gas element such as nitrogen, argon gas prevent entering of air, water vapor.
2), because the speed of the isotope exchange reaction of heavy oxygen water and the temperature of reaction have direct relation, certain relation is also had with the reaction times.When temperature of reaction is too high, the non-reaction loss of heavy oxygen water is serious, and reaction times too short then isotopic exchange effect is poor, therefore, in order to reduce the non-reaction loss of heavy oxygen water, simultaneously in the present invention
18the abundance requirement of O-oxoethanoic acid, by great many of experiments, determine that the temperature of isotope exchange reaction controls at 20 ~ 80 DEG C, the reaction times is 0.5 ~ 3 day.
3), this invention sodium hydroxide heavy oxygen aqueous solution used put in the heavy oxygen water of certain abundance by caustic soda to produce, and the sodium hydroxide chemical formula in the method gained sodium hydroxide heavy oxygen aqueous solution is Na
18oH, in follow-up isotope exchange reaction, compares common aqueous sodium hydroxide solution, contained by it
18the forward that OH-is conducive to isotope exchange reaction carries out.
Compared with prior art, the invention has the beneficial effects as follows: the oxoethanoic acid of natural abundance 0.204% is carried out Oxygen isotope exchange reaction with heavy oxygen water by the present invention after purifying in reactor, finally can to obtain abundance is 1% ~ 99%
18o-oxoacetic acid product.Present invention process is simple, and easy and simple to handle, less energy consumption, product purity is high, H
2 18o loss is few.
Accompanying drawing explanation
Fig. 1 is preparation
18the device schematic diagram of O-crystal oxoethanoic acid;
In figure: the cold and hot thermostatic bath of 1-, 2-reactor, 3-vacuum buffer tank, 4-thermometer, 5-condenser, 6-receiving flask.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Fig. 1 is preparation
18the device schematic diagram of O-crystal oxoethanoic acid.Be first that 1000:1 ~ 1000:10 puts into reactor 2 by a certain amount of crystal oxoethanoic acid and appropriate sodium hydroxide heavy oxygen water according to oxoethanoic acid and sodium hydroxide mol ratio, reactor 2 is placed in cold and hot thermostatic bath 1.The inner set temperature meter 4 of reactor 2, shielding gas is entered in reactor 2 by vacuum buffer tank 3.15 ~ 40 DEG C, fill protection airtight condition of closing under reaction 10 ~ 60 minutes; Constantly interval underpressure distillation concentrates subsequently, vacuum tightness is at 20 ~ 95KPa, initial stage distillation temperature 15 ~ 90 DEG C, until solution simmer down to original 15% ~ 60% time reduce rapidly cold and hot thermostatic bath 1 temperature to 5 ~-5 DEG C, now mass crystallization is had to occur in reactor 2, temperature keeps 1-3 hour, with sufficient crystallising.Subsequently material in reactor 2 is realized solid-liquid separation by whizzer, get its solid portion and put into loft drier and dry and obtain the crystal oxoethanoic acid after purifying, the heavy oxygen current steamed are recovered in receiving flask 6 after condenser 5; Purified crystals oxoethanoic acid and high abundance heavy oxygen water are put into reactor according to the mol ratio of 1:5 ~ 1:100 and carries out Oxygen isotope exchange reaction, fill protection gas in reactor, temperature controls at 20 ~ 80 DEG C, reacts 0.5 ~ 10 day; By interval underpressure distillation condensing crystal after reaction terminates, vacuum tightness is at 20 ~ 95KPa, and distillation temperature 15 ~ 90 DEG C, the heavy oxygen Water Sproading steamed is in receiving flask.
Embodiment 1
A kind of
18the preparation method of O-crystal oxoethanoic acid, this preparation method specifically comprises the following steps:
(1) sodium hydroxide heavy oxygen water (abundance 90%) solution of the 1mol/L of crystal oxoethanoic acid 10mol, 0.1L of purity 85% is put into reaction kettle for reaction.Fill nitrogen in reactor, temperature controls at 35 DEG C, and the reaction times was at 30 minutes.
(2) underpressure distillation concentrates, temperature 50 C, vacuum tightness 32KPa.Until liquid concentration to original volume 30% time rapidly temperature is reduced to 0 DEG C, now have mass crystallization to occur.Insulation crystallization 1 hour, realizes solid-liquid separation by whizzer, gets the loft drier inner drying that solids is placed with nitrogen filling, obtains the crystal oxoethanoic acid 4.5mol after purifying.Heavy oxygen water is reclaimed by receiving flask.
(3) the crystal oxoethanoic acid 4.5mol after purifying and 50mol abundance 90% heavy oxygen water are put into the permutoid reaction that reactor carries out oxygen isotope, fill nitrogen in reactor, temperature of reaction 60 DEG C, the time is 3 days.
(4) underpressure distillation condensing crystal: vacuum tightness 60KPa, distillation temperature 45 DEG C.Heavy oxygen Water Sproading is in receiving flask.By the purity of titration of potassium permanganate oxoethanoic acid, by its abundance of organic mass spectrometry.Acquisition purity 96%,
18o abundance is 50%
18o-crystal oxoethanoic acid.
Embodiment 2
A kind of
18the preparation method of O-crystal oxoethanoic acid, this preparation method specifically comprises the following steps:
(1) sodium hydroxide heavy oxygen water (abundance 92%) solution of the 1.2mol/L of crystal oxoethanoic acid 20mol, 0.15L of purity 90% is put into reaction kettle for reaction.Fill argon shield gas in reactor, temperature controls at 40 DEG C, and the reaction times was at 45 minutes.
(2) underpressure distillation concentrates, temperature 45 C, vacuum tightness 68KPa.Until liquid concentration to original volume 20% time rapidly temperature is reduced to 1 DEG C, now have mass crystallization to occur.Insulation crystallization 2.1 hours, by whizzer, gets solids and puts into loft drier inner drying, obtains the crystal oxoethanoic acid 8mol after purifying.Heavy oxygen water is reclaimed by receiving flask.
(3) the crystal oxoethanoic acid 8mol after purifying and 100mol abundance 98% heavy oxygen water are put into the permutoid reaction that reactor carries out oxygen isotope, fill argon gas in reactor, temperature of reaction 60 DEG C, the time is 2 days.
(4) underpressure distillation condensing crystal: vacuum tightness 68KPa, distillation temperature 42 DEG C.Heavy oxygen Water Sproading is in receiving flask.By the purity of titration of potassium permanganate oxoethanoic acid, by its abundance of organic mass spectrometry.Acquisition purity 97%,
18o abundance is 70%
18o-crystal oxoethanoic acid.
Embodiment 3
A kind of
18the preparation method of O-crystal oxoethanoic acid, this preparation method specifically comprises the following steps:
(1) sodium hydroxide heavy oxygen water (abundance 90%) solution of the 1mol/L of crystal oxoethanoic acid 10mol, 0.1L of purity 85% is put into reaction kettle for reaction.Fill nitrogen protection gas in reactor, temperature controls at 35 DEG C, and the reaction times was at 30 minutes.
(2) underpressure distillation concentrates, temperature 50 C, vacuum tightness 32KPa.Until liquid concentration to original solution volume 30% time rapidly temperature is reduced to 0 DEG C, now have mass crystallization to occur.Insulation crystallization 1 hour, by whizzer, gets the loft drier inner drying that solids is placed with nitrogen filling, obtains the crystal oxoethanoic acid 4.5mol after purifying.Heavy oxygen water is reclaimed by receiving flask.
(3) the crystal oxoethanoic acid 4.5mol after purifying and 50mol abundance 80% heavy oxygen water are put into the permutoid reaction that reactor carries out oxygen isotope, fill nitrogen in reactor, temperature of reaction 60 DEG C, the time is 0.5 day.
(4) underpressure distillation condensing crystal: vacuum tightness 68KPa, distillation temperature 42 DEG C.Heavy oxygen Water Sproading is in receiving flask.By the purity of titration of potassium permanganate oxoethanoic acid, by its abundance of organic mass spectrometry.Acquisition purity 85%,
18o abundance is 20%
18o-crystal oxoethanoic acid.
Embodiment 4
A kind of
18the preparation method of O-crystal oxoethanoic acid, this preparation method specifically comprises the following steps:
(1) sodium hydroxide heavy oxygen water (abundance 92%) solution of the 1mol/L of crystal oxoethanoic acid 2mol, 0.018L of purity 90% is put into reaction kettle for reaction.Fill argon shield gas in reactor, temperature controls at 40 DEG C, 45 minutes reaction times.
(2) underpressure distillation concentrates, temperature 45 C, vacuum tightness 68KPa.Until liquid concentration to original solution volume 40% time rapidly temperature is reduced to 1 DEG C, now have mass crystallization to occur.Insulation crystallization 2.1 hours, by whizzer, gets solids and puts into loft drier inner drying, obtains the crystal oxoethanoic acid 1.5mol after purifying.Heavy oxygen water is reclaimed by receiving flask.
(3) the crystal oxoethanoic acid 1.5mol after purifying and 15mol abundance 97% heavy oxygen water are put into the permutoid reaction that reactor carries out oxygen isotope, fill argon gas in reactor, temperature of reaction 70 DEG C, the time is 15 days.
(4) underpressure distillation condensing crystal: vacuum tightness 68KPa, distillation temperature 42 DEG C.Heavy oxygen Water Sproading is in receiving flask.Obtain purity 97%, abundance be 60% anhydrous
18o-crystal oxoethanoic acid.
(5) the crystal oxoethanoic acid of acquisition and 15mol abundance 97% heavy oxygen water are put into the permutoid reaction that reactor carries out oxygen isotope again, fill argon gas in reactor, temperature of reaction 70 DEG C, the time is 15 days.
(6) underpressure distillation condensing crystal: vacuum tightness 68KPa, distillation temperature 42 DEG C.Heavy oxygen Water Sproading is in receiving flask.By the purity of titration of potassium permanganate oxoethanoic acid, by its abundance of organic mass spectrometry.Acquisition purity 97%,
18o abundance is 90%
18o-crystal oxoethanoic acid.
Embodiment 5
A kind of
18the preparation method of O-crystal oxoethanoic acid, the method comprises the following steps:
(1) by common crystal oxoethanoic acid (
18o is natural abundance 0.204%, purity is 70%), a small amount of sodium hydroxide heavy oxygen aqueous solution puts into reaction kettle for reaction, helium filled by reactor, temperature controls at 15 ~ 20 DEG C, reaction times was at 50 ~ 60 minutes, crystal oxoethanoic acid and sodium hydroxide molar ratio are 1000:1, and sodium hydroxide heavy oxygen aqueous solution volumetric molar concentration is 1mol/L;
(2) vacuumize underpressure distillation after reaction to concentrate, temperature is at 55 DEG C, pressure vacuum degree is at 20-25KPa, rapidly temperature is reduced to 0 to-5 DEG C until liquid concentration to during the 15%-20% of original solution volume, then crystallization 1-3 hour is incubated, after solid-liquid separation, get the loft drier inner drying that solids is placed with helium filling, obtain the crystal oxoethanoic acid after purifying.
(3) by the crystal oxoethanoic acid after purifying with
18the abundance of O be 5% heavy oxygen water put into the permutoid reaction that reactor carries out oxygen isotope, fill helium in reactor, temperature of reaction controls at 20 ~ 30 DEG C, for adding fast response, can be aided with stirring, the reaction times is 3 days, the molar ratio of crystal oxoethanoic acid and heavy oxygen water controls, at 1:5, to obtain
18the O-oxoethanoic acid heavy oxygen aqueous solution;
(4), after reaction terminates, underpressure distillation condensing crystal, temperature is 15-20 DEG C, and vacuum tightness is 20 ~ 25KPa, obtains
18o-crystal oxoethanoic acid, reclaims the heavy oxygen water of evaporation simultaneously.By the purity of titration of potassium permanganate oxoethanoic acid, by its abundance of organic mass spectrometry, obtained
18o-crystal oxoethanoic acid abundance is 1%, and purity is 70%.
Embodiment 6
A kind of
18the preparation method of O-crystal oxoethanoic acid, the method comprises the following steps:
(1) by common crystal oxoethanoic acid (
18o is natural abundance 0.204%, purity is 99.9%), a small amount of sodium hydroxide heavy oxygen aqueous solution puts into reaction kettle for reaction, argon gas filled by reactor, temperature controls at 35 ~ 40 DEG C, reaction times was at 10 ~ 20 minutes, crystal oxoethanoic acid and sodium hydroxide molar ratio are 100:1, and sodium hydroxide heavy oxygen aqueous solution volumetric molar concentration is 5mol/L;
(2) vacuumize underpressure distillation after reaction to concentrate, temperature range is at 45 DEG C, pressure vacuum degree is at 90-95KPa, rapidly temperature is reduced to 0 to 5 DEG C until liquid concentration to during the 55%-60% of original solution volume, then crystallization 1-3 hour is incubated, after solid-liquid separation, get the loft drier inner drying that solids is placed with argon gas filling, obtain the crystal oxoethanoic acid after purifying.
(3) by the crystal oxoethanoic acid after purifying with
18the abundance of O is that 99% heavy oxygen water puts into the permutoid reaction that reactor carries out oxygen isotope, and fill argon gas in reactor, temperature of reaction controls at 80 DEG C, for adding fast response, can be aided with stirring, the reaction times is 0.5 day, the molar ratio of crystal oxoethanoic acid and heavy oxygen water controls, at 1:100, to obtain
18the O-oxoethanoic acid heavy oxygen aqueous solution;
(4), after reaction terminates, underpressure distillation condensing crystal, temperature is 70 DEG C, and vacuum tightness is 90 ~ 95KPa, obtains
18o-crystal oxoethanoic acid, reclaims the heavy oxygen water of evaporation simultaneously;
(5) repeat step (2) and obtain more high abundance (3) 3 times with step
18o-crystal oxoethanoic acid.By the purity of titration of potassium permanganate oxoethanoic acid, by its abundance of organic mass spectrometry, finally obtain
18o-crystal oxoethanoic acid abundance is 99%, and purity is 99.9%.
Embodiment 7
A kind of
18the preparation method of O-crystal oxoethanoic acid, this preparation method specifically comprises the following steps:
(1) sodium hydroxide heavy oxygen water (abundance 98%) solution of the 1mol/L of crystal oxoethanoic acid 4mol, 0.036L of purity 90% is put into reaction kettle for reaction.Fill argon shield gas in reactor, temperature controls at 40 DEG C, 45 minutes reaction times.
(2) underpressure distillation concentrates, temperature 45 C, vacuum tightness 68KPa.Until liquid concentration to original solution volume 40% time rapidly temperature is reduced to 1 DEG C, now have mass crystallization to occur.Insulation crystallization 2.1 hours, by whizzer, gets solids and puts into loft drier inner drying, obtains the crystal oxoethanoic acid 2.8mol after purifying.Heavy oxygen water is reclaimed by receiving flask.
(3) the crystal oxoethanoic acid 2.8mol after purifying and 30mol abundance 98% heavy oxygen water are put into the permutoid reaction that reactor carries out oxygen isotope, fill argon gas in reactor, temperature of reaction 70 DEG C, the time is 15 days.
(4) underpressure distillation condensing crystal: vacuum tightness 68KPa, distillation temperature 42 DEG C.Heavy oxygen Water Sproading is in receiving flask.
(5) the crystal oxoethanoic acid of acquisition and 30mol abundance 98% heavy oxygen water are put into the permutoid reaction that reactor carries out oxygen isotope again, fill argon gas in reactor, temperature of reaction 70 DEG C, the time is 15 days.
(6) underpressure distillation condensing crystal: vacuum tightness 68KPa, distillation temperature 42 DEG C.Heavy oxygen Water Sproading is in receiving flask.
(7) repeat step (5) and obtain more high abundance (6) 2 times with step
18o-crystal oxoethanoic acid.
By the purity of titration of potassium permanganate oxoethanoic acid, by its abundance of organic mass spectrometry.Acquisition purity 97%,
18o abundance is 98%
18o-crystal oxoethanoic acid.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. one kind
18the preparation method of O-crystal oxoethanoic acid, it is characterized in that, the method comprises the following steps:
(1) common crystal oxoethanoic acid is added recrystallization in the sodium hydroxide heavy oxygen aqueous solution, obtain the crystal oxoethanoic acid after purifying;
(2) the crystal oxoethanoic acid after purifying and heavy oxygen water are put into the permutoid reaction that reactor carries out oxygen isotope; protection gas is filled in reactor; temperature of reaction controls at 20 ~ 80 DEG C; reaction times is 0.5 ~ 3 day; the molar ratio of crystal oxoethanoic acid and heavy oxygen water controls, at 1:5 ~ 1:100, to obtain
18the O-oxoethanoic acid heavy oxygen aqueous solution;
(3), after reaction terminates, underpressure distillation condensing crystal, obtains
18o-crystal oxoethanoic acid;
(4) repeating step (2) obtains more abundant with step (3)
18o-crystal oxoethanoic acid.
2. one according to claim 1
18the preparation method of O-crystal oxoethanoic acid, is characterized in that, step (4) obtains
18o-crystal oxoethanoic acid abundance is 1% ~ 99%, and purity is 70% ~ 99.9%.
3. one according to claim 2
18the preparation method of O-crystal oxoethanoic acid, is characterized in that, step (4) obtains
18o-crystal oxoethanoic acid abundance is 50% ~ 99%.
4. one according to claim 1
18the preparation method of O-crystal oxoethanoic acid, is characterized in that, step (4) obtains
18o-crystal oxoethanoic acid exists with the form of a water oxoethanoic acid, anhydrous oxoethanoic acid or hypocrystalline water oxoethanoic acid.
5. one according to claim 1
18the preparation method of O-crystal oxoethanoic acid, is characterized in that, the common crystal oxoethanoic acid purity described in step (1) is 70% ~ 99.9%, exists with the form of a water oxoethanoic acid, anhydrous oxoethanoic acid or hypocrystalline water oxoethanoic acid.
6. one according to claim 1
18the preparation method of O-crystal oxoethanoic acid, is characterized in that, the method for carrying out recrystallization in step (1) is specially:
A common crystal oxoethanoic acid, a small amount of sodium hydroxide heavy oxygen aqueous solution are put into reaction kettle for reaction by (), protection gas filled by reactor, temperature controls at 15 ~ 40 DEG C, reaction times was at 10 ~ 60 minutes, crystal oxoethanoic acid and sodium hydroxide molar ratio are 1000:(1 ~ 10), sodium hydroxide heavy oxygen aqueous solution volumetric molar concentration is 1 ~ 5mol/L;
Vacuumize underpressure distillation after (b) reaction to concentrate; temperature range is at 45 ~ 55 DEG C; pressure vacuum degree is at 20-95KPa; rapidly temperature is reduced to 5 to-5 DEG C until liquid concentration to during the 15%-60% of original solution volume; then crystallization 1-3 hour is incubated; after solid-liquid separation, get the loft drier inner drying that solids is placed with the filling of protection gas, obtain the crystal oxoethanoic acid after purifying.
7. one according to claim 1
18the preparation method of O-crystal oxoethanoic acid, is characterized in that, in the heavy oxygen water described in step (2)
18the abundance scope of O is 5% ~ 99%.
8. one according to claim 1
18the preparation method of O-crystal oxoethanoic acid, is characterized in that, in step (3), during underpressure distillation condensing crystal, temperature is 15-90 DEG C, and vacuum tightness is 20 ~ 95KPa.
9. the one according to claim 1 or 6
18the preparation method of O-crystal oxoethanoic acid, is characterized in that, described protection gas is helium, neon, argon gas, xenon or nitrogen.
10. the one according to claim 1 or 6
18the preparation method of O-crystal oxoethanoic acid, is characterized in that, the sodium hydroxide heavy oxygen aqueous solution described in step (1) is obtained by sodium Metal 99.5 and the reaction of high abundance heavy oxygen water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410804848.XA CN104557516B (en) | 2014-12-18 | 2014-12-18 | A kind of18The preparation method of O-crystal oxoethanoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410804848.XA CN104557516B (en) | 2014-12-18 | 2014-12-18 | A kind of18The preparation method of O-crystal oxoethanoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104557516A true CN104557516A (en) | 2015-04-29 |
| CN104557516B CN104557516B (en) | 2016-06-01 |
Family
ID=53074699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410804848.XA Active CN104557516B (en) | 2014-12-18 | 2014-12-18 | A kind of18The preparation method of O-crystal oxoethanoic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104557516B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935850A (en) * | 2017-12-04 | 2018-04-20 | 上海化工研究院有限公司 | A kind of synthetic method of the nipagin esters of stable isotope 18O marks |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462946A (en) * | 2008-12-30 | 2009-06-24 | 上海华谊（集团）公司 | Method for preparing ethanol acid by catalytic oxidation of biformyl |
| US7993931B1 (en) * | 2003-10-28 | 2011-08-09 | Quest Diagnostics Investments Incorporated | Oxygen-18 labeled organic acids and use in diagnosing metabolic disorders |
-
2014
- 2014-12-18 CN CN201410804848.XA patent/CN104557516B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7993931B1 (en) * | 2003-10-28 | 2011-08-09 | Quest Diagnostics Investments Incorporated | Oxygen-18 labeled organic acids and use in diagnosing metabolic disorders |
| CN101462946A (en) * | 2008-12-30 | 2009-06-24 | 上海华谊（集团）公司 | Method for preparing ethanol acid by catalytic oxidation of biformyl |
Non-Patent Citations (2)
| Title |
|---|
| INGRID CHRISTIANSEN,ET AL.,: "Microwave spectra of isotopic glyoxylic acids,structure and intramolecular hydrogen bond", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
| KEITH L.CLAY,ET AL.,: "The Exchange of [18O]-H2O with the Aromatic Oxygen Atoms of Catecholamine Metabolites", 《BIOMEDICAL MASS SPECTROMETRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935850A (en) * | 2017-12-04 | 2018-04-20 | 上海化工研究院有限公司 | A kind of synthetic method of the nipagin esters of stable isotope 18O marks |
| CN107935850B (en) * | 2017-12-04 | 2020-12-29 | 上海化工研究院有限公司 | Synthesis method of stable isotope 18O-labeled nipagin ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104557516B (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2016184055A1 (en) | Process method for extracting magnesium and lithium from brine and coproducing hydrotalcite | |
| Xing et al. | Rubidium extraction from mineral and brine resources: A review | |
| CN105536707A (en) | Material for separating lithium isotope, preparation method and application thereof | |
| CN108545775A (en) | A method of detaching tungsten from the ammonium tungstate solution of high molybdenum content | |
| CN104085857A (en) | New method for preparing high-purity hydroiodic acid | |
| CN104557516B (en) | A kind of18The preparation method of O-crystal oxoethanoic acid | |
| CN103818942B (en) | Method for preparing high-purity anhydrous strontium iodide | |
| CN104829481A (en) | Preparation method of N,N,N',N'-tetraoctyl-3-oxa pentanediamide | |
| CN103950950A (en) | Preparation method of boron-11 acid with high abundance | |
| CN102863023B (en) | Synthesis and purification method of electronic grade arsines | |
| CN109775760B (en) | Ultra-low potassium ammonium molybdate solution, ammonium molybdate solution derivative product and preparation method thereof | |
| CN102690299B (en) | Method for preparing sucralose-6-acetate by tandem reaction | |
| CN106565455B (en) | Electron level malonic acid | |
| CN103601240B (en) | Preparation method of silver hexafluoroantimonate | |
| CN101575089B (en) | Method for preparing <18>O-nitric acid | |
| CN202558637U (en) | Novel lithium hexafluorophosphate production device | |
| CN110002475A (en) | The preparation method of lithium hydroxide | |
| CN113772733B (en) | Water phase preparation method of anhydrous uranyl chloride | |
| CN105417556A (en) | Preparation method of ammonium bifluoride | |
| CN107902679A (en) | A kind of industrial method for producing battery-level lithium carbonate | |
| CN101569799A (en) | Method for producing oxygen-18 gas and deuterium gas by using natural water | |
| CN108070907A (en) | A kind of method that bittern of dried-up lake prepares basic magnesium chloride whisker | |
| CN103159175A (en) | High-conversion-rate germane preparation method | |
| CN107777668A (en) | A kind of preparation method of demercuration bromide | |
| CN104276605B (en) | A kind of preparation method of monoclinic phase molybdenum trioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 200062 Shanghai city Putuo District Yunling Road No. 345 Co-patentee after: Shanghai Lianhong Isotope Technology Co., Ltd. Patentee after: Shanghai Chemical Research Institute Co., Ltd. Address before: 200062 Shanghai city Putuo District Yunling Road No. 345 Co-patentee before: Shanghai Lianhong Isotope Technology Co., Ltd. Patentee before: Shanghai Research Institute of Chemical Industry |
|
| CP01 | Change in the name or title of a patent holder |