CN102206236A - Metal cyanide made from organic nitrile and preparation method thereof - Google Patents
Metal cyanide made from organic nitrile and preparation method thereof Download PDFInfo
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- CN102206236A CN102206236A CN2010101367927A CN201010136792A CN102206236A CN 102206236 A CN102206236 A CN 102206236A CN 2010101367927 A CN2010101367927 A CN 2010101367927A CN 201010136792 A CN201010136792 A CN 201010136792A CN 102206236 A CN102206236 A CN 102206236A
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- cyclohexanediamine
- salicylic aldehyde
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- 150000002825 nitriles Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 title claims abstract description 14
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 14
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 231100000053 low toxicity Toxicity 0.000 claims description 4
- 125000006850 spacer group Chemical group 0.000 claims description 4
- DISHRDNUYGLDMW-UHFFFAOYSA-N 3,6-dioxocyclohexa-1,4-diene-1-carbonitrile methane Chemical compound C.C.O=C1C=CC(=O)C(=C1)C#N DISHRDNUYGLDMW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 abstract description 7
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004880 explosion Methods 0.000 abstract description 2
- 239000002262 Schiff base Substances 0.000 abstract 1
- 150000004753 Schiff bases Chemical class 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229940097267 cobaltous chloride Drugs 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical class [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Abstract
The invention discloses metal cyanide made from organic nitrile and a preparation method thereof. In the method, metal salt, organic nitrile and Schiff base are dissolved in an organic solvent, after full stirring and heating, the target product can be obtained. According to the invention, virulent raw materials like hydrogen cyanide, potassium cyanide and sodium cyanide are avoided, and substances like peroxides easy to result in explosions are not generated during reactions. In addition, lump crystal product can be obtained in one-step reaction directly. Thus, the method of the invention is safe and efficient.
Description
[technical field]
The present invention relates to a kind of metal cyanides that directly makes by organic nitrile and preparation method thereof.
[background technology]
Metal cyanides is widely used in fields such as Industrial Catalysis, mining, organic syntheses, but its preparation process is but relatively more dangerous.Because traditional method for preparing metal cyanides, general hypertoxic cyanic acid, potassium cyanide, the sodium cyanides etc. of all using are as reaction raw materials, as with prussic acid, milk of lime, ferrous sulfate or iron protochloride being raw material one step generation ferrocyanide calcium solution, alkaline ferro prussiate that this solution obtains expecting with the corresponding alkali metal salts reaction again or the like, concrete preparation process is referring to CN87106254A, US3247258, US4477589, US447256, US5188952, EP283148 etc.
The synthesis technique of the cyano group cobalt acid potassium of bibliographical information adopts with cobaltous chloride and potassium cyanide synthetic method more.CA55 rolls up 10187 disclosed preparation methods and 15% excessive slightly cobaltous chloride solution is splashed in 15% potassium cyanide solution reaction generate the inferior cobalt precipitation of cyaniding, again with the excessive slightly potassium cyanide reaction of the inferior cobalt copper of cyaniding, concentrate, crystallization, filter product.In its preparation process, if aerobic conditions generates Potassium peroxide, oxygen free condition then generates hydrogen, and there is explosion hazard in system.Simultaneously, operator easily touch the inferior cobalt of potassium cyanide, cyaniding and the filtrate of severe toxicity, have bigger potential safety hazard.
Therefore, it is of far-reaching significance to look for the method for preparing metal cyanides safely and effectively.
[summary of the invention]
The object of the invention provides a kind of reaction raw materials such as hypertoxic prussic acid, potassium cyanide, sodium cyanide that replaced by the low toxicity organic nitrile to prepare the method for metal cyanides.Present method directly is dissolved in the organic solvent with metal-salt, organic nitrile, Schiff's base, stirs, and heating, single step reaction obtains metal cyanides.
The inventive method technical scheme is:
1. the metal cyanides that is directly made by the low toxicity organic nitrile, it is characterized in that: its chemical formula is: K
2[LCo (CN)
2]
22CH
3OH, molecular weight are 997.94, and wherein L is N, and N '-two (salicylic aldehyde) contracts-1R, 2R-cyclohexanediamine or N, N '-two (salicylic aldehyde) cyclohexanediamine that contracts; When L is N, N '-two (salicylic aldehyde) contracts-1R, and during the 2R-cyclohexanediamine, crystal data: monocline, spacer are P2 (1),
β=92.82 (1) °,
, Z=2; When L is N, when N '-two (salicylic aldehyde) contracted cyclohexanediamine, crystal data: three is oblique, and spacer is P-1,
C=21.788 (7),
, β=89.87 (1) °, γ=78.21 (1) °,
, Z=2.。
2, a kind of preparation method according to item 1 described metal cyanides comprises the steps:
A) cobalt salt of equivalent, Schiff's base, organic nitrile are dissolved in the organic solvent, fully stirring and evenly mixing;
B) in the reactor that mixing liquid is added, heating, constant temperature, cooling;
C) filter, wash, promptly get target product.
3. according to item 2 described preparation methods, it is characterized in that: described cobalt salt is a Cobaltous diacetate.
4. according to item 2 described preparation methods, it is characterized in that: described Schiff's base is N, N '-two (salicylic aldehyde) contract cyclohexanediamine or N, and N '-two (salicylic aldehyde) contracts-1R, the 2R-cyclohexanediamine.
5. according to item 2 described preparation methods, it is characterized in that: described organic nitrile is TCNQ, and TCNQ is 7,7,8,8-four cyano benzoquinone bismethane.
6. according to item 2 described preparation methods, it is characterized in that: described organic solvent is meant methyl alcohol.
7. according to item 2 described preparation methods, it is characterized in that: reactant heats in reactor in the step b), and temperature is 70 ℃-80 ℃.
8. according to item 2 described preparation methods, it is characterized in that: reactant heats in reactor in the step b), and constant temperature time is 1.5-3 days.
9. according to item 2 described preparation methods, it is characterized in that: after reactant heats in reactor in the step b), programmed cooling 6-50 hour.
This method is the raw material low toxicity not only, can not generate superoxide etc. in the reaction process and easily cause the material that explodes, and single step reaction directly obtains the bulk crystals product, and is more safe and efficient.Can be used for fields such as Industrial Catalysis, mining, organic synthesis.
[description of drawings]
Fig. 1 prussiate crystalline structure (chirality L part)
Fig. 2 prussiate crystalline structure (achirality L part)
[embodiment]
Below in conjunction with accompanying drawing embodiments of the invention are elaborated.Present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
Take by weighing successively Cobaltous diacetate (0.2mmol, 0.0498g), N, N '-two (salicylic aldehyde) contracts-1R, the 2R-cyclohexanediamine (0.2mmol, 0.0644g), (0.2mmol 0.0408g) is dissolved in the 8ml methyl alcohol KTCNQ, magnetic agitation one hour, fully mixing joins in the reactor, temperature programming 4 hours to 80 ℃, is incubated 3 days, programmed cooling 33 hours, suction filtration, water, methanol wash respectively, vacuum-drying gets red bulk crystals product, and productive rate is 34.72%.
Embodiment 2;
Take by weighing successively Cobaltous diacetate (0.2mmol, 0.0498g), N, N '-two (salicylic aldehyde) cyclohexanediamine (0.2mmol that contracts, 0.0644g), (0.2mmol 0.0408g) is dissolved in the 8ml methyl alcohol KTCNQ, magnetic agitation one hour, fully mixing joins in the reactor, temperature programming 4 hours to 80 ℃, is incubated 3 days, programmed cooling 33 hours, suction filtration, water, methanol wash respectively, vacuum-drying gets red bulk crystals product, and productive rate is 49.60%.
Claims (9)
1. the metal cyanides that is directly made by the low toxicity organic nitrile, it is characterized in that: its chemical formula is: K
2[LCo (CN)
2]
22CH
3OH, molecular weight are 997.94, and wherein L is N, and N '-two (salicylic aldehyde) contracts-1R, 2R-cyclohexanediamine or N, N '-two (salicylic aldehyde) cyclohexanediamine that contracts; When L is N, N '-two (salicylic aldehyde) contracts-1R, and during the 2R-cyclohexanediamine, crystal data: monocline, spacer are P2 (1), a=13.969 (1)
B=8.164 (5)
C=19.974 (3)
β=92.82 (1) °, V=2275 (3)
Z=2; When L is N, when N '-two (salicylic aldehyde) contracted cyclohexanediamine, crystal data: three is oblique, and spacer is P-1, a=8.202 (3)
B=13.449 (1)
C=21.788 (7),
α=89.96 (1) °, β=89.87 (1) °, γ=78.21 (1) °, V=2352 (3)
Z=2.。
2. the preparation method of a metal cyanides according to claim 1 comprises the steps:
A) cobalt salt of equivalent, Schiff's base, organic nitrile are dissolved in the organic solvent, fully stirring and evenly mixing;
B) in the reactor that mixing liquid is added, heating, constant temperature, cooling;
C) filter, wash, promptly get target product.
3. preparation method according to claim 2 is characterized in that: described cobalt salt is a Cobaltous diacetate.
4. preparation method according to claim 2 is characterized in that: described Schiff's base is N, N '-two (salicylic aldehyde) contract cyclohexanediamine or N, and N '-two (salicylic aldehyde) contracts-1R, the 2R-cyclohexanediamine.
5. preparation method according to claim 2 is characterized in that: described organic nitrile is TCNQ, and TCNQ is 7,7,8,8-four cyano benzoquinone bismethane.
6. preparation method according to claim 2 is characterized in that: described organic solvent is meant methyl alcohol.
7. preparation method according to claim 2, it is characterized in that: reactant heats in reactor in the step b), and temperature is 70 ℃-80 ℃.
8. preparation method according to claim 2, it is characterized in that: reactant heats in reactor in the step b), and constant temperature time is 1.5-3 days.
9. preparation method according to claim 2 is characterized in that: after reactant heats in reactor in the step b), and programmed cooling 6-50 hour.
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| CN2010101367927A CN102206236A (en) | 2010-03-31 | 2010-03-31 | Metal cyanide made from organic nitrile and preparation method thereof |
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| CN2010101367927A CN102206236A (en) | 2010-03-31 | 2010-03-31 | Metal cyanide made from organic nitrile and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015062459A1 (en) * | 2013-10-28 | 2015-05-07 | 浙江大学 | Method for synthesizing metal cyanide through fenton reagent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4477589A (en) * | 1982-03-31 | 1984-10-16 | Shell Oil Company | Catalysts for the polymerization of epoxides and process for the preparation of such catalysts |
-
2010
- 2010-03-31 CN CN2010101367927A patent/CN102206236A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4477589A (en) * | 1982-03-31 | 1984-10-16 | Shell Oil Company | Catalysts for the polymerization of epoxides and process for the preparation of such catalysts |
Non-Patent Citations (5)
| Title |
|---|
| GULLOTTI MICHELE ET AL.: "Optically active complexes of Schiff bases. Part 3. Complexes of iron(III) with quadridentate Schiff bases derived from salicylaldehyde", 《JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS》 * |
| MARTIN C. GROSSEL ET AL.: "An Investigation of the Factors that Influence the Decomposition of 7,7",8,8’-Tetracyanoquinodimethane (TCNQ) and Its Salts to, and Structural Characterization of, the r,r-Dicyano-p-toluoylcyanide Anion", 《CHEMISTRY OF MATERIALS》 * |
| PASINI, A ET AL.: "Low spin iron(III) complexes with tetradentate Schiff bases", 《INORGANIC AND NUCLEAR CHEMISTRY LETTERS》 * |
| WAI-LUN MAN ET AL.: "General Synthesis of (Salen)ruthenium(III) Complexes via N· · · N Coupling of (Salen)ruthenium(VI) Nitrides", 《INORGANIC CHEMISTRY》 * |
| Y FUJII ET AL.: "INTERLIGAND INTERACTIONS FOR N-UNIDENTATE AMINO ACIDATE IN TRANS-[CO ((R, R)-SAL2CHXN)(CN)(AMINO ACIDATO)]-", 《THE CHEMICAL SCOCIETY OF JAPAN》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015062459A1 (en) * | 2013-10-28 | 2015-05-07 | 浙江大学 | Method for synthesizing metal cyanide through fenton reagent |
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Application publication date: 20111005 |