CN109206459A - A kind of preparation method of four ammonia platinum (II) of acetic acid - Google Patents
A kind of preparation method of four ammonia platinum (II) of acetic acid Download PDFInfo
- Publication number
- CN109206459A CN109206459A CN201811094140.4A CN201811094140A CN109206459A CN 109206459 A CN109206459 A CN 109206459A CN 201811094140 A CN201811094140 A CN 201811094140A CN 109206459 A CN109206459 A CN 109206459A
- Authority
- CN
- China
- Prior art keywords
- platinum
- acetic acid
- ammonia
- ammonia platinum
- solution
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 162
- QSKKXNSTGHZSQB-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.[Pt+2] QSKKXNSTGHZSQB-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 63
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 21
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000001639 calcium acetate Substances 0.000 claims abstract description 16
- 235000011092 calcium acetate Nutrition 0.000 claims abstract description 16
- 229960005147 calcium acetate Drugs 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 15
- LEAMURMBTFQRNZ-UHFFFAOYSA-N azanide;oxalic acid;platinum(2+) Chemical compound [NH2-].[NH2-].[Pt+2].OC(=O)C(O)=O LEAMURMBTFQRNZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229910014813 CaC2 Inorganic materials 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004176 ammonification Methods 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007858 starting material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- XKUTVNLXHINPAP-UHFFFAOYSA-N azane platinum Chemical compound N.[Pt] XKUTVNLXHINPAP-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 description 2
- -1 platinum (II) class compounds Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- QSDSNNSKORVORL-UHFFFAOYSA-N acetic acid;silver Chemical compound [Ag].CC(O)=O QSDSNNSKORVORL-UHFFFAOYSA-N 0.000 description 1
- 229940095054 ammoniac Drugs 0.000 description 1
- UMWYYMCOBYVEPY-UHFFFAOYSA-N azanide;platinum(2+) Chemical compound [NH2-].[NH2-].[Pt+2] UMWYYMCOBYVEPY-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
- C07F15/0093—Platinum compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of four ammonia platinum (II) of acetic acid.The preparation method comprises the following steps: ammonium chloroplatinate (IV) is successively generated acetic acid four ammonia platinum (II) solution through three-step reaction with oxalic acid, ammonium hydroxide, calcium acetate, last four ammonia platinum (II) solution of acetic acid is precipitated to obtain acetic acid four ammonia platinum (II) crystal by solvent crystal after concentration, then the vacuum dried four ammonia platinum (II) of acetic acid for obtaining purity and being >=99.95%.Starting material ammonium chloroplatinate (IV) is the Conventional compounds of platinum in the present invention, and raw material is easy to get and yield is high, other auxiliary material oxalic acid, concentrated ammonia liquor and calcium acetate are cheap, greatly reduce production cost；In addition, this method not only avoids the residual of chloride ion and nitrate ion, the residual of silver ion in product is also reduced.The present invention carries out at normal temperatures and pressures, easy to operate, easily controllable, reaction yield height (> 92%), and product purity height (>=99.95%) is suitable for the batch and industrial production of four ammonia platinum (II) of acetic acid.
Description
Technical field
The invention belongs to chemical catalysis technical fields, and in particular to a kind of preparation method of four ammonia platinum (II) of acetic acid.
Background technique
Platinum catalyst is widely used in the every field such as petrochemical industry, medication chemistry, vehicle exhaust and environmental improvement, and by
The residual of chloride ion and nitrate ion in the precursor compound for prepare platinum catalyst, influences the high temperature resistant of platinum catalyst
The service life of performance, activity and equipment, increasing with its dosage, requirement of the people to platinum catalyst is higher and higher,
The lower require the residual of chloride ion and nitrate ion the better.
Four ammino platinum (II) class compounds are a kind of important platinum (II) compounds, are widely used in chemical catalysis and plating
Industry.Wherein acetic acid four ammonia platinum (II) (Pt (NH3)4(CH3COO)2) it is highly soluble in water, it is organic molten insoluble in alcohols, ketone etc.
Agent is that solubility is highest in current four ammoniac compounds of mainstream, is very suitable to infusion process and prepares platinum catalyst, because of its aqueous solution
Containing acetate, buffering can be played the role of simultaneously, also there is the research for being used as electroplating main salt, so four ammonia platinum (II) of acetic acid
It is increasingly becoming a kind of important platinum lead compound.The patent of Publication No. CN103113412A discloses a kind of without chlorine and nitre
Water-soluble Pt (II) catalyst precursor and its synthetic method of sour silver, which passed through using tetraammineplatinum chloride as starting material
Four ammino platinum of target compound acetic acid is obtained with acetic acid silver reaction.Since tetraammineplatinum chloride is not easy to obtain in this method, cost
Higher and yield is not high；In addition silver acetate price is more expensive, and dosage is larger, and the disadvantages of remaining silver ion is easy in product,
Therefore, which is restricted.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of four ammonia platinum (II) of acetic acid, starting material chlorine platinum in this method
Sour ammonium (IV) is the Conventional compounds of platinum, and raw material is easy to get and yield is high, other auxiliary material oxalic acid, concentrated ammonia liquor and calcium acetate price are just
Preferably, production cost can be reduced；In addition, this method is not only avoided that the residual of chloride ion and nitrate ion, moreover it is possible to reduce product
The residual of middle silver ion.
To achieve the above object, a kind of preparation method of four ammonia platinum (II) of acetic acid, by ammonium chloroplatinate (IV) successively with oxalic acid,
Ammonium hydroxide, calcium acetate generate four ammonia platinum (II) of acetic acid after three-step reaction, then after solvent crystal, drying, and specific reaction step is as follows:
(1) ammonium chloroplatinate (IV) is restored to obtain oxalic acid diamino platinum (II) solution with oxalic acid, reaction equation is as follows:
(NH4)2PtCl6+2H2C2O4=Pt (NH3)2(C2O4)+6HCl+2CO2
(2) oxalic acid diamino platinum (II) is transformed into oxalic acid four ammonia platinum (II) solution through concentrated ammonia liquor ammonification, and reaction equation is as follows:
Pt(NH3)2(C2O4)+2NH3·H2O=Pt (NH3)4(C2O4)+2H2O
(3) calcium acetate is added in four ammonia platinum (II) of oxalic acid and obtains four ammonia platinum (II) solution of acetic acid and calcium oxalate, reaction equation
It is as follows:
Pt(NH3)4(C2O4)+Ca(CH3COO)2=Pt (NH3)4(CH3COO)2+CaC2O4
(4) by solvent crystal is precipitated to obtain four ammonia platinum of acetic acid after concentrated by rotary evaporation after the filtering of four ammonia platinum (II) solution of acetic acid
(II) crystal, then the vacuum dried four ammonia platinum (II) of acetic acid for obtaining purity and being >=99.95%.
Preferably, the mass ratio of ammonium chloroplatinate (IV) and oxalic acid is 1:(0.4~0.7 in step (1)), reaction temperature 30
~50 DEG C.
Preferably, the mass ratio of step (2) mesoxalic acid diamino platinum (II) and concentrated ammonia liquor is 1:(3~5), it is anti-to stir lower control
Answer temperature at 50~60 DEG C.
Preferably, the weight ratio of four ammonia platinum (II) of step (3) mesoxalic acid and calcium acetate is 1:(1~1.2).
Preferably, acetic acid four ammonia platinum (II) solution that step (4) obtains is filtered to remove insoluble matter, and filtrate is directly concentrated under reduced pressure
Concentrate is obtained, concentrate is added in alcohols or organic solvent of ketone under stiring, obtains white crystals, alcohols or ketone have
The volume of solvent and the volume ratio of acetic acid four ammonia platinum (II) solution are (15~20): 1, after white crystals are filtered and are washed
50~80 DEG C of vacuum drying, obtain four ammonia platinum (II) of acetic acid.
Compared with prior art, in the present invention starting material ammonium chloroplatinate (IV) be platinum Conventional compounds, raw material is easy to get
And yield is high, other auxiliary material oxalic acid, concentrated ammonia liquor and calcium acetate are cheap, greatly reduce production cost；In addition, this method
The residual for not only avoiding chloride ion and nitrate ion also reduces the residual of silver ion in product.The vinegar of this method preparation
Sour four ammonia platinum (II) have very high water solubility, and dissociation reaction occurs for the compound in aqueous solution, release stable with sun
Ion Pt (NH3)4 2+, be conducive to carrier adsorption precursor compound when dipping, in addition, also containing acetate, energy in its aqueous solution
Play the role of buffering simultaneously, also there is the research for being used as electroplating main salt.The method of the present invention carries out at normal temperatures and pressures, operation
Simply, easily controllable, reaction yield height (> 92%), product purity height (>=99.95%) is suitable for four ammonia platinum (II) of acetic acid
Batch and industrial production.
Specific embodiment
Invention is further described in detail with reference to embodiments.
Embodiment one
A kind of preparation method of four ammonia platinum (II) of acetic acid, comprising the following steps:
4.0g (0.044mol) oxalic acid is weighed into 300mL beaker, 50mL deionized water is added, then stirring and dissolving is delayed
It is slow that 10.0g (0.023mol) ammonium chloroplatinate solid is added by several times, it is stirred to react 2h at 30 DEG C, there is a little undissolved solid, is stopped
Stirring stands 10min filtering, obtains oxalic acid diamino platinum (II) solution (7.3g).Slowly add in oxalic acid diamino platinum (II) solution
Enter ammonium hydroxide 25mL (22.7g), controls temperature at 50~60 DEG C, react 2h, stop heating, be cooled to room temperature, take 8g calcium acetate molten
Solution is allowed to dissolve in 25mL deionized water, is then slowly added to calcium acetate solution into oxalic acid four ammonia platinum (8.0g) solution, until
It is rear that 5mL acetic acid is added until not generating precipitating, continue to stir 0.5h, stands 30min, obtain four ammonia platinum solution of acetic acid and white
Calcium oxalate, filtering are precipitated, and is washed 2 times with appropriate amount of deionized water, is concentrated under reduced pressure to give after filtrate and wash water merging at 80 DEG C
The concentrate of 15mL adds 3mL acetic acid, and the concentrate for having acetic acid then will be added and be added in 300mL methanol solution, be precipitated
White crystals obtain four ammonia platinum of 7.95g acetic acid, yield 92.2% in 50~80 DEG C of dry 2h after filtering and being washed with methanol.It produces
Product examine is surveyed: chlorinity 7.6ppm.
Carry out elemental analysis, infrared spectroscopy detection, the detection of hydrogen spectrum and carbon spectrum detection, structure respectively by the sample to preparation
Characteristic parameter are as follows: (1) elemental analysis: measured value C 12.52%, H 4.65%, N 14.6%, Pt 50.98%, with theoretical value C
12.59%, H 4.76%, N 14.69%, Pt 51.17% are consistent.(2)IR(cm-1, KBr) and 3259,3220 (s, v (NH3))；
1695,1653 (s, vas(C=O)).1406 (s, vs(C=O)).(3)1HNMR(D2O, ppm) 1.75 (s, 3H, CH3)。(4)13C
NMR(D2O, ppm) 23.7 (CH3), 181.9 (COO).These above-mentioned parameters meet the chemical structure of invented compound.
Embodiment two
A kind of preparation method of four ammonia platinum (II) of acetic acid, comprising the following steps:
50.0g (0.555mol) oxalic acid is weighed into 2000mL beaker, addition 600mL deionized water, stirring and dissolving, then
100.0g (0.225mol) ammonium chloroplatinate solid is slowly added by several times, 1.5h is stirred to react at 40 DEG C, stops stirring, stands
10min filtering, obtains oxalic acid diamino platinum (II) solution (71.3g).Ammonium hydroxide is slowly added in oxalic acid diamino platinum (II) solution
320mL (291g) controls temperature at 50~60 DEG C, reacts 2h, stops heating, be cooled to room temperature, 86.9g calcium acetate is taken to be dissolved in
It in 300mL deionized water, is allowed to dissolve, then calcium acetate solution is slowly added into oxalic acid four ammonia platinum (79.0g) solution, until not
It is rear that 30mL acetic acid is added until generating precipitating, continue to stir 0.5h, stand 30min, obtains four ammonia platinum solution of acetic acid and white is heavy
Shallow lake calcium oxalate, filtering, and washed 2 times with appropriate amount of deionized water, 100mL is concentrated under reduced pressure to give at 80 DEG C after filtrate and wash water merging
Concentrate, add 5mL acetic acid, then will be added have acetic acid concentrate be added in 2000mL methanol solution, be precipitated it is white
Color crystallization obtains four ammonia platinum of 80.06g acetic acid, yield 92.8% in 50~80 DEG C of dry 2h after filtering and being washed with methanol.It produces
Product examine is surveyed: chlorinity 7.2ppm.
Carry out elemental analysis, infrared spectroscopy detection, the detection of hydrogen spectrum and carbon spectrum detection, structure respectively by the sample to preparation
Characteristic parameter are as follows: (1) elemental analysis: measured value C 12.54%, H 4.63%, N 14.62%, Pt 50.96%, with theoretical value
C 12.59%, H 4.76%, N 14.69%, Pt 51.17% are consistent.(2)IR(cm-1, KBr) and 3259,3220 (s, v
(NH3))；1695,1653 (s, vas(C=O)).1406 (s, vs(C=O)).(3)1HNMR(D2O, ppm) 1.75 (s, 3H, CH3)。
(4)13C NMR(D2O, ppm) 23.7 (CH3),181.9(COO).These parameters meet the chemical structure of invented compound.
Embodiment three
A kind of preparation method of four ammonia platinum (II) of acetic acid, comprising the following steps:
140g (1.555mol) oxalic acid is weighed into 5000mL beaker, addition 1000mL deionized water, stirring and dissolving, then
200g (0.451mol) ammonium chloroplatinate solid is slowly added by several times, 1h is stirred to react at 50 DEG C, stops stirring, stands 10min mistake
Filter, obtains oxalic acid diamino platinum (II) solution (143.0g).Ammonium hydroxide 785mL is slowly added in oxalic acid diamino platinum (II) solution
(715g) controls temperature at 50~60 DEG C, reacts 3h, stop heating, be cooled to room temperature, 190g calcium acetate is taken to be dissolved in 600mL
It in deionized water, is allowed to dissolve, then calcium acetate solution is slowly added into oxalic acid four ammonia platinum (158.3g) solution, until not generating
It is rear that 50mL acetic acid is added until precipitating, continue to stir 0.5h, stand 30min, obtains four ammonia platinum solution of acetic acid and white precipitate grass
Sour calcium, filtering, and washed 2 times with appropriate amount of deionized water, the dense of 180mL is concentrated under reduced pressure to give at 80 DEG C after filtrate and wash water merging
Contracting liquid adds 10mL acetic acid, and the concentrate for having acetic acid then will be added and be added in 3000mL acetone soln, white knot is precipitated
Crystalline substance obtains four ammonia platinum of 159.6g acetic acid, yield 92.84% in 50~80 DEG C of dry 2h after filtering and being washed with methanol.Product inspection
It surveys: chlorinity 7.4ppm.
Carry out elemental analysis, infrared spectroscopy detection, the detection of hydrogen spectrum and carbon spectrum detection, structure respectively by the sample to preparation
Characteristic parameter are as follows: (1) elemental analysis: measured value C 12.56%, H 4.62%, N 14.60%, Pt 51.06%, with theoretical value
C 12.59%, H 4.76%, N 14.69%, Pt 51.17% are consistent.(2)IR(cm-1, KBr) and 3259,3220 (s, v
(NH3))；1695,1653 (s, vas(C=O)).1406 (s, vs(C=O)).(3)1HNMR(D2O, ppm) 1.75 (s, 3H, CH3)。
(4)13C NMR(D2O, ppm) 23.7 (CH3),181.9(COO).These parameters meet the chemical structure of invented compound.
Claims (5)
1. a kind of preparation method of four ammonia platinum (II) of acetic acid, which is characterized in that by ammonium chloroplatinate (IV) successively with oxalic acid, ammonium hydroxide,
Calcium acetate generates four ammonia platinum (II) of acetic acid after three-step reaction, then after solvent crystal, drying, and specific reaction step is as follows:
(1) ammonium chloroplatinate (IV) is restored to obtain oxalic acid diamino platinum (II) solution with oxalic acid, reaction equation is as follows:
(NH4)2PtCl6+2H2C2O4=Pt (NH3)2(C2O4)+6HCl+2CO2
(2) oxalic acid diamino platinum (II) is transformed into oxalic acid four ammonia platinum (II) solution through concentrated ammonia liquor ammonification, and reaction equation is as follows:
Pt(NH3)2(C2O4)+2NH3·H2O=Pt (NH3)4(C2O4)+2H2O
(3) addition calcium acetate obtains four ammonia platinum (II) solution of acetic acid in four ammonia platinum (II) of oxalic acid and calcium oxalate, reaction equation are as follows:
Pt(NH3)4C2O4+Ca(CH3COO)2=Pt (NH3)4(CH3COO)2+CaC2O4
(4) by solvent crystal is precipitated to obtain acetic acid four ammonia platinum (II) crystalline substance after concentrated by rotary evaporation after the filtering of four ammonia platinum (II) solution of acetic acid
Body, then the vacuum dried four ammonia platinum (II) of acetic acid for obtaining purity and being >=99.95%.
2. a kind of preparation method of four ammonia platinum (II) of acetic acid according to claim 1, which is characterized in that chlorine in step (1)
The mass ratio of platinic acid ammonium (IV) and oxalic acid is 1:(0.4~0.7), reaction temperature is 30~50 DEG C.
3. a kind of method for preparing four ammonia platinum (II) of acetic acid according to claim 1 or 2, which is characterized in that in step (2)
The mass ratio of oxalic acid diamino platinum (II) and concentrated ammonia liquor is 1:(3~5), lower control reaction temperature is stirred at 50~60 DEG C.
4. a kind of preparation method of four ammonia platinum (II) of acetic acid according to claim 1 or 2, which is characterized in that in step (3)
The weight ratio of four ammonia platinum (II) of oxalic acid and calcium acetate is 1:(1~1.2).
5. a kind of preparation method of four ammonia platinum (II) of acetic acid according to claim 1 or 2, which is characterized in that step (4)
To acetic acid four ammonia platinum (II) solution be filtered to remove insoluble matter, filtrate is directly concentrated under reduced pressure to give concentrate, under stiring will be dense
Contracting liquid is added in alcohols or organic solvent of ketone, obtains white crystals, the volume and four ammonia of acetic acid of alcohols or organic solvent of ketone
The volume ratio of platinum (II) solution is (15~20): 1, it is dried in vacuo, obtains at 50~80 DEG C after white crystals are filtered and washed
Four ammonia platinum (II) of acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811094140.4A CN109206459B (en) | 2018-09-19 | 2018-09-19 | Preparation method of tetraammineplatinum acetate (II) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811094140.4A CN109206459B (en) | 2018-09-19 | 2018-09-19 | Preparation method of tetraammineplatinum acetate (II) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109206459A true CN109206459A (en) | 2019-01-15 |
| CN109206459B CN109206459B (en) | 2021-03-02 |
Family
ID=64984609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811094140.4A Active CN109206459B (en) | 2018-09-19 | 2018-09-19 | Preparation method of tetraammineplatinum acetate (II) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109206459B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897070A (en) * | 2019-02-28 | 2019-06-18 | 徐州浩通新材料科技股份有限公司 | A kind of preparation method of four ammonia palladium (II) of acetic acid |
| CN112939100A (en) * | 2021-03-15 | 2021-06-11 | 徐州浩通新材料科技股份有限公司 | Preparation method of tetraammine palladium (II) bicarbonate |
| CN113278034A (en) * | 2021-05-14 | 2021-08-20 | 昆明贵金属研究所 | Water-soluble Pt (IV) complex and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1631980A1 (en) * | 1988-10-21 | 1996-09-27 | МГУ им. М.В.Ломоносова | Process for preparing oxalatodiaminoplatinum (ii) |
| CN101255176A (en) * | 2008-04-03 | 2008-09-03 | 昆明贵金属研究所 | Novel precursor compound for preparing platinum-carrying catalyst and synthetic method thereof |
| CN101389637A (en) * | 2006-01-30 | 2009-03-18 | 普拉托技术（私有）公司 | Preparation of platinum (ll) complexes |
| CN103113412A (en) * | 2013-01-31 | 2013-05-22 | 昆明贵金属研究所 | Water soluble Pt(II) catalyst precursor free from chlorine and nitrate and synthetic method thereof |
-
2018
- 2018-09-19 CN CN201811094140.4A patent/CN109206459B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1631980A1 (en) * | 1988-10-21 | 1996-09-27 | МГУ им. М.В.Ломоносова | Process for preparing oxalatodiaminoplatinum (ii) |
| CN101389637A (en) * | 2006-01-30 | 2009-03-18 | 普拉托技术（私有）公司 | Preparation of platinum (ll) complexes |
| CN101255176A (en) * | 2008-04-03 | 2008-09-03 | 昆明贵金属研究所 | Novel precursor compound for preparing platinum-carrying catalyst and synthetic method thereof |
| CN103113412A (en) * | 2013-01-31 | 2013-05-22 | 昆明贵金属研究所 | Water soluble Pt(II) catalyst precursor free from chlorine and nitrate and synthetic method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897070A (en) * | 2019-02-28 | 2019-06-18 | 徐州浩通新材料科技股份有限公司 | A kind of preparation method of four ammonia palladium (II) of acetic acid |
| CN109897070B (en) * | 2019-02-28 | 2021-06-18 | 徐州浩通新材料科技股份有限公司 | Preparation method of tetraamminepalladium acetate (II) |
| CN112939100A (en) * | 2021-03-15 | 2021-06-11 | 徐州浩通新材料科技股份有限公司 | Preparation method of tetraammine palladium (II) bicarbonate |
| CN112939100B (en) * | 2021-03-15 | 2021-11-09 | 徐州浩通新材料科技股份有限公司 | Preparation method of tetraammine palladium (II) bicarbonate |
| CN113278034A (en) * | 2021-05-14 | 2021-08-20 | 昆明贵金属研究所 | Water-soluble Pt (IV) complex and preparation method and application thereof |
| CN113278034B (en) * | 2021-05-14 | 2022-07-08 | 昆明贵金属研究所 | Water-soluble Pt (IV) complex and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109206459B (en) | 2021-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109206459A (en) | A kind of preparation method of four ammonia platinum (II) of acetic acid | |
| CN109897070A (en) | A kind of preparation method of four ammonia palladium (II) of acetic acid | |
| CN103395847B (en) | The synthetic method of sulphuric acid four ammino palladium | |
| CA2492254C (en) | Process for the preparation of 1,2-diaminocyclohexane-platinum(ii) complexes | |
| CN112225757B (en) | Preparation method of lobaplatin trihydrate | |
| WO2007085957A1 (en) | Preparation of platinum (ll) complexes | |
| CN101367557A (en) | Novel method for synthesis of tetrammine platinum hydrogen nitrate (II) | |
| CN103467528B (en) | A kind of preparation method of lobaplatin | |
| CN113173607B (en) | Synthesis method of trichloro ammine potassium platinate | |
| Parker et al. | Interactions of vanadium (IV) with amidoxime ligands: redox reactivity | |
| CN110604742A (en) | Eucommia polysaccharide strontium complex and preparation method and application thereof | |
| RU2482916C2 (en) | CARBOXYLATE COMPOUNDS OF NOBLE METALS Ir, Ru, Rh, Pd, Pt AND Au, HAVING HIGH CATALYTIC EFFICIENCY | |
| CN106632548A (en) | High-purity troxerutin and preparation method thereof | |
| CN101362781A (en) | Synthesis method of tetraammine palladium (II) oxalate | |
| CN114106052B (en) | Tetranuclear platinum carboxylate, synthesis method and application thereof in preparation of platinum black | |
| CN112897600B (en) | Preparation method of tetraamminepalladium sulfate (II) | |
| KR20180057103A (en) | Preparation method of ruthenium compound and ruthenium compound thereby | |
| RU2367610C1 (en) | Method for preparation of cis-dichloroamonoplatinum (ii) | |
| KR102080239B1 (en) | Novel method of preparing Epinastine | |
| CN114478648A (en) | Pyridine-like pyrrole ruthenium complex, preparation method thereof and application of complex as electrocatalytic ammonia oxidation catalyst | |
| CN109574097B (en) | Preparation method of trichloro-hexa-amino ruthenium | |
| JP3287562B2 (en) | Method for producing tetraammineplatinum complexes | |
| RU2309158C1 (en) | Method for production of cis-dichloroamminisopropylamine platinum(ii) | |
| CN113185464B (en) | Preparation method of zinc histidine | |
| CN114853636B (en) | Preparation method of peramivir intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |