CN105968058A - Hydrothermal synthesis method of 3,5-diamino-1,2,4-triazole - Google Patents
Hydrothermal synthesis method of 3,5-diamino-1,2,4-triazole Download PDFInfo
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- CN105968058A CN105968058A CN201610298448.5A CN201610298448A CN105968058A CN 105968058 A CN105968058 A CN 105968058A CN 201610298448 A CN201610298448 A CN 201610298448A CN 105968058 A CN105968058 A CN 105968058A
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- triazole
- cyanamide
- copper
- ammonium salt
- ammonium
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 12
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 title abstract 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 37
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 69
- 239000007787 solid Substances 0.000 claims description 35
- 238000000605 extraction Methods 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 19
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 15
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 15
- 208000035126 Facies Diseases 0.000 claims description 13
- BVWCKYAYMBDPIP-UHFFFAOYSA-N NC=1C=C(C=C(C1)N)C=CC1=CC=CC=C1 Chemical compound NC=1C=C(C=C(C1)N)C=CC1=CC=CC=C1 BVWCKYAYMBDPIP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 239000000543 intermediate Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 239000002360 explosive Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 239000001166 ammonium sulphate Substances 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 claims description 2
- ZIPLUEXSCPLCEI-UHFFFAOYSA-N cyanamide group Chemical group C(#N)[NH-] ZIPLUEXSCPLCEI-UHFFFAOYSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000002574 poison Substances 0.000 claims 1
- 231100000614 poison Toxicity 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 20
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 abstract description 11
- 229940123208 Biguanide Drugs 0.000 abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 abstract description 10
- 238000009833 condensation Methods 0.000 abstract description 8
- 230000005494 condensation Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 5
- 238000006482 condensation reaction Methods 0.000 abstract description 4
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 abstract 3
- 239000005750 Copper hydroxide Substances 0.000 abstract 3
- 229910001956 copper hydroxide Inorganic materials 0.000 abstract 3
- 239000012467 final product Substances 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- HUUBMTMJIQHAEN-UHFFFAOYSA-N triazole-1,4-diamine Chemical compound NC1=CN(N)N=N1 HUUBMTMJIQHAEN-UHFFFAOYSA-N 0.000 abstract 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- 238000001914 filtration Methods 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- -1 aminoguanidine thiourea Chemical compound 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 10
- 239000000284 extract Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- 150000004699 copper complex Chemical class 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 150000001912 cyanamides Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- 241000736199 Paeonia Species 0.000 description 2
- 235000006484 Paeonia officinalis Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical compound NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/14—Nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a hydrothermal synthesis method of 3,5-diamino-1,2,4-triazole. The method comprises the following steps: cyan substituted derivatives, ammonium salt, copper hydroxide and water are used as raw materials, hydrothermal synthesis is carried out in a condition with high pressure, and 3,5-diamino-1,2,4-triazole is obtained. Cyanamide, ammonium salt, and copper hydroxide are used as raw materials, a high pressure reaction apparatus is used, ammonia which is decomposed from the ammonium salt in the effects of copper hydroxide and two molecules of cyanamide are condensed, in order to generate a copper biguanide complex. Copper(I) sulfide is eliminated from the copper biguanide complex in a condition with existence of sulfide, and 3,5-diamino-triazole is obtained by a cyclocondensation reaction. A high pressure reaction vessel is used for increasing the concentration of ammonia in a water system, which is good for generation of the condensation reaction, and at the same time, time and temperature required for condensation of cyanamide are effectively reduced. Existence of excess ammonium salt is used, in order to stabilize the pH value of the whole reaction system, and generation of the side reaction of polymerization of cyanamide is avoided. The method has the advantages of simple process, low raw material cost, and high purity of the final product.
Description
Technical field
The invention belongs to organic synthesis field, particularly to a kind of 3,5-diaminostilbene, 2,4-triazole hydrothermal synthesis methods.
Background technology
3,5-diaminourea 1,2,4-triazoles, English writes a Chinese character in simplified form (DAT), is a kind of important fine chemicals intermediate.It
It is many based on 1,2,4-triazole pharmaceutical chemicals synthetic intermediates, produce in medicine, dyestuff, pesticide, sterilization and daily use chemicals
Product have a wide range of applications.Based on 1, the metal complex of 5-diaminourea triazole, due to the multiformity of its structure, shows
Abundant optics, electricity and magnetic performance, is the functional material that has a extensive future of a class.DAT is also a kind of important simultaneously
Explosive intermediate feed.
United States Patent (USP) 2648671 discloses a kind of 3 in nineteen fifty-three, the synthesis technique (see Fig. 1) of 5-diaminourea triazole: with water
For solvent, after dicyandiamide and hydrazine hydrochloride directly being mixed under 40 degrees celsius, utilize the heat that reaction produces self, permissible
Fast reaction obtains 3, and the thick product of 5-diaminourea triazole, thick product is after methanol extraction purifies desalination, and overall yield is permissible
Reach 97%.But finding in follow-up application and research process, due to 3,5-diaminourea triazole itself is soluble in water, its
Purity is the highest due to the salt containing a large amount of ease of solubilities for product.(Wang Baizhou, Jia Siyuan in experimentation follow-up report in detail
Deng, chemical reagent, 2007), the actual recovery of this method is not above 90%.At PCT Patent WO2002060881 in 2002
In, use Hydrazinium sulfate to replace hydrazine hydrochloride, thick product yield is about 75%, and owing to wherein salinity is high, purifies difficulty high.
1963, Frankel et al. reported synthetic method (the Rrankel M.B.et al.Journal of with dicyandiamide barium as raw material
Inorganic Chemistry, 1963.) (see Fig. 2).Dicyandiamide barium and high concentration hydrazine hydrate react in normal-temperature water solution, add sulfur
After acid filters out barium sulfate precipitate, evaporation and concentration obtains 3, and 5-diaminourea triazole, thick product yield is up to 81.3%.But dicyandiamide
Barium does not has commercialization, this technique to be difficult to industrialized production.
Additionally, by aminoguanidine thiourea (Godfrey, L.E.A.et al.J.chem.Soc. (London) 1960.；Kurzer,F.et al.
Angew.Chem.intrrnat.Edit.1963. see Fig. 3), N-cyano group-O-methyl-isourea (Zmitek, Janko, Vestnik Slovenskega
Kemijskega rustva, 1992, is shown in Fig. 4) etc. condensation reaction can also obtain corresponding 3,5-diaminourea derivant.But
The raw materials used costliness of these synthetic methods, does not has significant practical applications.
2013, Wei Qing et al. reported a kind of 3, the synthetic method of 5-bis-replacement 1,2,4-triazole derivatives (Wei Qing,
Et al.Synthetic Communications, 2013, see Fig. 5).This method utilizes cyano group substitutive derivative, liquefied ammonia, sulphuric acid
Copper and a small amount of water under microwave or condition of high voltage 140 degrees Celsius of reactions, it is possible to obtain 3,5-bis-replacements 1,2,4-tri-
Nitrogen Zole derivatives closes copper complex, and then reflux in ammonium sulfide solution removing cuprous sulfide by this coordination compound, it is possible to obtain corresponding
3,5-bis-substituted 1,2,4-triazole derivant.This method can obtain the yield close to 80% under microwave condition.But at Wei
In the report of Qing et al., the yield under condition of high voltage is the most relatively low, less than 30%.
Summary of the invention
In order to overcome above-mentioned deficiency, the invention provides one and feed intake simplicity, side reaction is few, and production cost is low, it is possible to realize work
The 3,5-diaminostilbene that industry metaplasia is produced, the synthesis technique of 2,4-triazole.
In order to overcome that Wei Qing et al. reports 3, the synthetic method of 5-bis-replacement 1,2,4-triazole derivatives (Wei Qing,
Et al.Synthetic Communications, 2013) problem that yield is relatively low under elevated pressure conditions, the present invention to its synthesis mechanism and
Limiting factor has carried out systematic analysis and great many of experiments, it is provided that use Copper hydrate to substitute copper sulfate, is providing the same of copper ion
Time promote the decomposition of ammonium salt, and then improve biguanide and close the generating rate of copper complex and reactivity.Result shows: condition of high voltage
The yield of lower product significantly improves (reaching more than 80%)；In final products, dicyandiamide by-product impurity content is decreased obviously.
On the other hand, experiment chances on: after using Copper hydrate to substitute copper sulfate, the reaction temperature of hydro-thermal reaction is by 140 DEG C
Being reduced to about 110 DEG C, this is possibly due to Copper hydrate and improves ammonia equilibrium concentration in aqueous systems, beneficially condensation reaction
Generation, effectively reduce simultaneously cyanamide condensation required for time and temperature.
For achieving the above object, the present invention uses following scheme:
A kind of 3,5-diaminostilbene, 2,4-triazole hydrothermal synthesis methods, including:
With cyano group substitutive derivative, ammonium salt, Copper hydrate and water as raw material, under elevated pressure conditions, Hydrothermal Synthesis 3,5-diamino
Base-1,2,4-triazole.
Preferably, the temperature of described Hydrothermal Synthesis is 110-120 DEG C, and the response time is 3-5 hour.
Preferably, described cyano group substitutive derivative is cyanamide.
Preferably, described cyano group substitutive derivative, ammonium salt, the thing mass ratio that feeds intake of Copper hydrate are 2:2.2-2.5:1.Three
If in cyanamide excess final products, dicyandiamide by-product impurity content is significantly raised in kind of raw material；Copper hydrate provide copper from
Also play a driving role for the decomposition of ammonium chloride while son, in whole reaction system can slightly excess, excess is too many to finally
Yield and quality the most do not affect.The amount of ammonium salt is relatively big on the impact of whole yield, and deficiency can make integral system yield be decreased obviously,
Serious excess also can affect final yield.Preferably feed intake the 2:1.2:1 that has a competition.
Preferably, described ammonium salt is ammonium hydrogen carbonate, oxalic acid ammonia, ammonium sulphate, ammonium chloride, Ammonium Acetate or ammonium dihydrogen phosphate.From one-tenth
Originally with actual effect preferably ammonium chloride.
Preferably, the concentration of described cyanamide aqueous solution is 30%-50%.Preferably 50%.
Preferably, described method specifically includes following steps:
Under high pressure, air-proof condition, it is sequentially added into Copper hydrate, ammonium salt and cyanamide aqueous solution, is heated to predetermined temperature and carries out
Reaction, after having reacted, is cooled to room temperature, obtains dark red solid；
In above-mentioned dark red solid, add sodium sulfide solution, be heated to reflux to producing red precipitate, filter, use dichloromethane
Organic facies in alkane extraction filtrate, decompression distillation, obtain white 3,5-diaminostilbene, 2,4-triazole solids.
Preferably, described sodium sulfide is 1:1 with the rate of charge of Copper hydrate.
Use 3,5-diaminostilbene prepared by any of the above-described method, 2,4-triazole.
The present invention prepare 3,5-diaminostilbene, the optics of 2,4-triazoles, electricity and magnetic performance are excellent, manufacture pharmaceutical chemicals
The field tools such as intermediate, dyestuff, pesticide, sterilization and daily chemical products or explosive intermediate are widely used.
Described cyanamide, ammonium salt, Copper hydrate, sodium sulfide, dichloromethane are chemical pure.
The present invention is with cyanamide, ammonium salt, and Copper hydrate is raw material, uses high pressure reaction assembly, utilizes ammonium salt to make at Copper hydrate
The ammonia decomposited under with and the condensation of two molecule cyanamides, generate biguanide and close copper complex.Biguanide is closed copper complex and is existed at sulfide
Under conditions of slough cuprous sulfide, contracting ring obtains 3,5-diaminourea triazole.
W-response says the exothermic process belonging to spontaneous from thermodynamics, but ammonia needs higher temperature with the condensation reaction of cyanamide
Degree.This technology effectively reduces the time required for cyanamide condensation and temperature.The ammonium salt utilizing excess exists, and can stablize whole
Precursor reactant system pH, it is to avoid the generation of cyanamide polymerization side reactions.
Present invention process is simple, and cost of material is low, and final products purity is high.
Beneficial effects of the present invention:
1, the present invention is to utilize autoclave, uses high pressure reaction assembly, utilizes ammonium salt to decomposite under Copper hydrate effect
Ammonia and the condensation of two molecule cyanamides, generate biguanide and close copper complex.Biguanide is closed copper complex and is sloughed under conditions of sulfide exists
Copper sulfide, contracting ring obtains 3,5-diaminourea triazole.Simplify the step of synthesis technique, decrease the generation of side reaction, it is ensured that
Product, to quality, improves productivity, reaction yield in terms of cyanamide higher than 80%.
2, the raw materials used cyanamide of the present invention, ammonium salt and Copper hydrate compare the dicyandiamide in traditional handicraft and hydrazine hydrochloride, cost
Low.In production technology, water consumption is little, and can be with recycled after separation cuprous sulfide.
3, the present invention utilizes biguanide to close after copper complex reacts with sulfide and extracts acquisition 3,5-diaminourea triazole, product purity
High.
4, step be simple and convenient to operate, practical.
Accompanying drawing explanation
Fig. 1 is that in prior art, dicyandiamide hydrazine hydrochloride method generates 3, the synthesis path figure of 5-diaminourea triazole；
Fig. 2 is that in prior art, cyanamide barium hydrazine hydrate method generates 3, the synthesis path figure of 5-diaminourea triazole；
Fig. 3 is that the aminoguanidine thiourea condensation process of document report generates 3, the synthesis path figure of 5-diaminourea triazole；
Fig. 4 is that the N-cyano group-O-methyl-isourea condensation process of document report generates 3, the synthesis path figure of 5-diaminourea triazole；
Fig. 5 is the cyanamide microwave treatment synthesis path figure of document report
Fig. 6 is the synthesis path figure of the present invention；
Fig. 7 is the synthesis mechanism figure that the present invention is possible
Fig. 8 is the embodiment of the present invention 1 synthetic product1HNMR spectrogram；
Fig. 9 is the FTIR spectrogram of the embodiment of the present invention 1 synthetic product；
Figure 10 is the high-efficient liquid phase chromatogram (chromatographic condition: detection wavelength 317nm of the embodiment of the present invention 1 synthetic product；Flowing
Mutually pure methanol；Test sample purity is higher than 98%)；
Figure 11 is the high-efficient liquid phase chromatogram (chromatographic condition: detection wavelength 317nm of comparative example of the present invention 2-in-1 one-tenth product；Flowing
Mutually pure methanol；Test sample purity is higher than 95%).
Detailed description of the invention
By the following examples feature of present invention and other correlated characteristic are described in further detail, in order to technology people of the same trade
The understanding of member:
The present invention is further described with embodiment below in conjunction with the accompanying drawings.
(1) being sequentially added into Copper hydrate, ammonium salt and cyanamide solution in 10L autoclave, its thing mass ratio that feeds intake is 1:
(1.2-1.5): 2, under sealing stirring, reactor is heated to 110 degrees Celsius, reacts 3 hours, after reaction terminates,
Slowly reduction reaction temperature is to room temperature, obtains dark red solid.
(2) being transferred in reactor after described red solid being filtered, adding mass concentration is 5% sodium sulfide solution, sodium sulfide
With the material amount that feeds intake of Copper hydrate only than for 1:1.After heating reflux reaction 20 minutes, mixed liquor is filtered to extraction through filter cylinder
Still, adds in filtrate with liquid volume than the dichloromethane for (05-0.7), extracts organic facies, obtain after being evaporated dichloromethane
White crystal, is dried through hot-air oven and i.e. can get 3,5-diaminourea triazole.
Below by instantiation, the present invention will be further elaborated, it should explanation, and following embodiment is merely to solve
Release the present invention, not its content is defined.
Embodiment 1:
(1) in 10L autoclave, it is sequentially added into Copper hydrate (98%) 2.5Kg, ammonium chloride (99%) 3.0Kg and list
Cyanamide (50%) 4.2Kg.Reactor for 1:2.2:2, under sealing stirring, is pressurizeed also by its material amount only ratio that feeds intake
Being to slowly warm up to 110 degrees Celsius, after reacting 3 hours, slowly reduction reaction temperature is to room temperature, obtains dark red solid after filtration.
(2) described red solid is transferred in 50L glass reaction still, adds the 25L aqueous solution dissolved with 1.4kg sodium sulfide
In.It is heated to reflux 30 minutes producing red precipitate, by mixed liquor through filter cylinder heat filtering to extraction kettle, extraction kettle adds 15L
Dichloromethane, extracts organic facies, obtains white solid after being evaporated dichloromethane, is dried i.e. available white 3,5-through hot-air oven
Diaminourea 1,2,4-triazole 2.2kg (with the cyanamide rate of collecting for 88%).
Embodiment 2:
(1) in 10L autoclave, it is sequentially added into Copper hydrate (98%) 2.5Kg, ammonium acetate (99%) 4.3Kg and list
Cyanamide (31%) 6.8Kg.Reactor for 1:2.2:2, under sealing stirring, is pressurizeed also by its material amount only ratio that feeds intake
Being to slowly warm up to 110 degrees Celsius, after reacting 3 hours, slowly reduction reaction temperature is to room temperature, obtains dark red solid after filtration.
(2) described red solid is transferred in 50L glass reaction still, adds the 25L aqueous solution dissolved with 1.4kg sodium sulfide
In.It is heated to reflux 30 minutes producing red precipitate, by mixed liquor through filter cylinder heat filtering to extraction kettle, extraction kettle adds 15L
Dichloromethane, extracts organic facies, obtains white solid after being evaporated dichloromethane, is dried i.e. available white 3,5-through hot-air oven
Diaminourea 1,2,4-triazole 2.2kg (with the cyanamide rate of collecting for 88%).
Embodiment 3:
(1) in 10L autoclave, it is sequentially added into Copper hydrate (98%) 2.5Kg, ammonium dihydrogen phosphate (99%) 6.4Kg
With cyanamide (31%) 6.8Kg.Reactor for 1:2.2:2, under sealing stirring, is added by its material amount only ratio that feeds intake
Pressing and be to slowly warm up to 110 degrees Celsius, after reacting 3 hours, slowly reduction reaction temperature is to room temperature, obtains peony after filtration
Solid.
(2) described red solid is transferred in 50L glass reaction still, adds the 25L aqueous solution dissolved with 1.4kg sodium sulfide
In.It is heated to reflux 30 minutes producing red precipitate, by mixed liquor through filter cylinder heat filtering to extraction kettle, extraction kettle adds 15L
Dichloromethane, extracts organic facies, obtains white solid after being evaporated dichloromethane, is dried i.e. available white 3,5-through hot-air oven
Diaminourea 1,2,4-triazole 1.75kg (with the cyanamide rate of collecting for 70%).
Embodiment 4:
(1) in 10L autoclave, it is sequentially added into Copper hydrate (98%) 2.5Kg, ammonium chloride (99%) 3.4Kg and list
Cyanamide (31%) 6.8Kg.Reactor for 1:2.5:2, under sealing stirring, is pressurizeed also by its material amount only ratio that feeds intake
Being to slowly warm up to 110 degrees Celsius, after reacting 3 hours, slowly reduction reaction temperature is to room temperature, obtains dark red solid after filtration.
(2) described red solid is transferred in 50L glass reaction still, adds the 25L aqueous solution dissolved with 1.4kg sodium sulfide
In.It is heated to reflux 30 minutes producing red precipitate, by mixed liquor through filter cylinder heat filtering to extraction kettle, extraction kettle adds 15L
Dichloromethane, extracts organic facies, obtains white solid after being evaporated dichloromethane, is dried i.e. available white 3,5-through hot-air oven
Diaminourea 1,2,4-triazole 2.05kg (with the cyanamide rate of collecting for 82%).
Embodiment 5:
(1) in 10L autoclave, it is sequentially added into Copper hydrate (98%) 2.5Kg, ammonium chloride (99%) 3.0Kg and list
Cyanamide (31%) 6.8Kg.Reactor for 1:2.2:2, under sealing stirring, is pressurizeed also by its material amount only ratio that feeds intake
Being to slowly warm up to 110 degrees Celsius, after reacting 5 hours, slowly reduction reaction temperature is to room temperature, obtains dark red solid after filtration.
(2) described red solid is transferred in 50L glass reaction still, adds the 25L aqueous solution dissolved with 1.4kg sodium sulfide
In.It is heated to reflux 30 minutes producing red precipitate, by mixed liquor through filter cylinder heat filtering to extraction kettle, extraction kettle adds 15L
Dichloromethane, extracts organic facies, obtains white solid after being evaporated dichloromethane, is dried i.e. available white 3,5-through hot-air oven
Diaminourea 1,2,4-triazole 2.1kg (with the cyanamide rate of collecting for 85%).
Embodiment 6:
(1) in 10L autoclave, it is sequentially added into Copper hydrate (98%) 2.5Kg, ammonium chloride (99%) 3.0Kg and list
Cyanamide (31%) 6.8Kg.Reactor for 1:2.2:2, under sealing stirring, is pressurizeed also by its material amount only ratio that feeds intake
Being to slowly warm up to 120 degrees Celsius, after reacting 3 hours, slowly reduction reaction temperature is to room temperature, obtains dark red solid after filtration.
(2) described red solid is transferred in 50L glass reaction still, adds the 25L aqueous solution dissolved with 1.4kg sodium sulfide
In.It is heated to reflux 30 minutes producing red precipitate, by mixed liquor through filter cylinder heat filtering to extraction kettle, extraction kettle adds 15L
Dichloromethane, extracts organic facies, obtains white solid after being evaporated dichloromethane, is dried i.e. available white 3,5-through hot-air oven
Diaminourea 1,2,4-triazole 2.15kg (with the cyanamide rate of collecting for 86%).
Embodiment 7:
(1) in 10L autoclave, it is sequentially added into Copper hydrate (98%) 2.5Kg, ammonium chloride (99%) 3.0Kg and list
Cyanamide (31%) 6.8Kg.Reactor for 1:2.2:2, under sealing stirring, is pressurizeed also by its material amount only ratio that feeds intake
Being to slowly warm up to 110 degrees Celsius, after reacting 3 hours, slowly reduction reaction temperature is to room temperature, obtains dark red solid after filtration.
(2) described red solid is transferred in 50L glass reaction still, adds the 25L aqueous solution dissolved with 1.4kg sodium sulfide
In.It is heated to reflux 30 minutes producing red precipitate, by mixed liquor through filter cylinder heat filtering to extraction kettle, extraction kettle adds 15L
Dichloromethane, extracts organic facies, obtains white solid after being evaporated dichloromethane, is dried i.e. available white 3,5-through hot-air oven
Diaminourea 1,2,4-triazole 2.1kg (with the cyanamide rate of collecting for 85%).
Contrast experiment 1:
(1) in 10L autoclave, copper sulfate (CuSO it is sequentially added into4·5H2O) 6.3Kg, liquefied ammonia (99%) 1.3Kg
With cyanamide (31%) 6.8Kg.Reactor for 1:3:2, under sealing stirring, is pressurizeed by its material amount only ratio that feeds intake
And it is to slowly warm up to 120 degrees Celsius, after reacting 48 hours, slowly reduction reaction temperature is to room temperature, obtains peony solid after filtration
Body.
(2) described red solid is transferred in 50L glass reaction still, adds the 25L aqueous solution dissolved with 1.8kg sodium sulfide
In.It is heated to reflux 30 minutes producing red precipitate, by mixed liquor through filter cylinder heat filtering to extraction kettle, extraction kettle adds 15L
Dichloromethane, extracts organic facies, obtains white solid after being evaporated dichloromethane, is dried i.e. available white 3,5-through hot-air oven
Diaminourea 1,2,4-triazole 0.5kg (with the cyanamide rate of collecting for 20%).
Contrast experiment 2:
(1) adding 500mL water at 2000ml there-necked flask, then 200.0g dicyandiamide is stirred vigorously 20 minutes and forms turbid liquid,
Again 155g Hydrazinium sulfate is added, and heat the mixture to 50 DEG C.The hydrazine hydrate 72ml of 80% concentration is added, and will reaction
Thing is heated to 120 DEG C to 125 DEG C, and period, all of solid slowly dissolved.Stirring reaction 16 hours at this temperature.At this moment
After between, a small amount of solid is had to separate out from solution.
(2), after reaction terminates, stop heating, reactant mixture is cooled to room temperature.Add the carbonic acid of 100mL 10% concentration
Sodium solution regulation pH value is to 9.Reactant is transferred in 2L separatory funnel, adds 500mL dichloromethane extraction organic facies,
Organic facies is dried with anhydrous sodium sulfate after washing, obtains white solid, be dried through hot-air oven after being evaporated dichloromethane
To white 3,5-diaminourea 1,2,4-triazole 169g (collecting rate 72% with dicyandiamide).
Result shows: using technical scheme synthesis 3,5-diaminourea 1,2,4-triazole is bright in comprehensive yield and cost
The aobvious production technology being better than existing document report.Embodiment, compared with comparative example, illustrates that the core of technical solution of the present invention uses
High pressure reaction assembly, utilizes ammonia and the condensation of two molecule cyanamides that ammonium salt decomposites under Copper hydrate effect, generates biguanide and close copper
Coordination compound.Biguanide is closed copper complex and is sloughed copper sulfide under conditions of sulfide exists, and contracting ring obtains 3,5-diaminourea triazole.
Copper hydrate, while promoting ammonium salt decomposition, provides copper ion for next step reflection so that the decomposition of ammonium salt and biguanide are closed copper and joined
The synthesis of compound can be worked in coordination with under hydrothermal conditions and be carried out.Simplify the step of synthesis technique.The existence of ammonium salt simultaneously is slow with ammonia
Punching effect stabilizes the acidity environment of reaction system, decreases the generation of cyanamide polymerization side reactions, it is ensured that product to quality,
Improve productivity, W-response yield in terms of cyanamide higher than 80%.
Finally should be noted that and the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, to the greatest extent
The present invention has been described in detail by pipe with reference to previous embodiment, and for a person skilled in the art, it still can be right
Technical scheme described in previous embodiment is modified, or wherein part is carried out equivalent.All spirit in the present invention
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.On
Although state and combine accompanying drawing the detailed description of the invention of the present invention is described, but not limiting the scope of the invention, institute
Belonging to skilled person and should be understood that on the basis of technical scheme, those skilled in the art need not pay creation
Property the various amendments that can make of work or deformation still within protection scope of the present invention.
Claims (10)
1. one kind 3,5-diaminostilbene, 2,4-triazole hydrothermal synthesis methods, it is characterised in that including:
With cyano group substitutive derivative, ammonium salt, Copper hydrate and water as raw material, under elevated pressure conditions, Hydrothermal Synthesis 3,5-diamino
Base-1,2,4-triazole.
2. the method for claim 1, it is characterised in that the temperature of described Hydrothermal Synthesis is 110-120 DEG C, the response time
For 3-5 hour.
3. the method for claim 1, it is characterised in that described cyano group substitutive derivative is cyanamide.
4. the method for claim 1, it is characterised in that described cyano group substitutive derivative, ammonium salt, the feeding intake of Copper hydrate
Ratio is 2:2.2-2.5:1.
5. the method for claim 1, it is characterised in that described ammonium salt is ammonium hydrogen carbonate, oxalic acid ammonia, ammonium sulphate, chlorination
Ammonium, Ammonium Acetate or ammonium dihydrogen phosphate.
6. the method for claim 1, it is characterised in that the concentration of described cyanamide aqueous solution is 30%-50%.
7. the method for claim 1, it is characterised in that described method specifically includes following steps:
Under high pressure, air-proof condition, it is sequentially added into Copper hydrate, ammonium salt and cyanamide aqueous solution, is heated to predetermined temperature and carries out
Reaction, after having reacted, is cooled to room temperature, obtains dark red solid；
In above-mentioned dark red solid, add sodium sulfide solution, be heated to reflux to producing red precipitate, filter, use dichloromethane
Organic facies in alkane extraction filtrate, decompression distillation, obtain white 3,5-diaminostilbene, 2,4-triazole solids.
8. method as claimed in claim 7, it is characterised in that described sodium sulfide is 1:1 with the rate of charge of Copper hydrate.
9. the 3,5-diaminostilbene that prepared by the method described in any one of claim 1-8,2,4-triazole.
10. the 3,5-diaminostilbene described in claim 9,2,4-triazole is manufacturing pharmaceutical chemicals intermediate, dyestuff, pesticide, is disappearing
Application in poison and daily chemical products or explosive intermediate, it is characterised in that described 3,5-diaminostilbene, 2,4-triazoles1H NMR
Spectrogram is as shown in Figure 8.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US2648671A (en) * | 1951-06-15 | 1953-08-11 | American Cyanamid Co | Preparation of guanazole |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2648671A (en) * | 1951-06-15 | 1953-08-11 | American Cyanamid Co | Preparation of guanazole |
Non-Patent Citations (3)
| Title |
|---|
| QING WEI ET AL.: "EFFICIENT IN SITU SYNTHESIS OF 3,5-DISUBSTITUTED-1,2,4-TRIAZOLES UNDER MICROWAVE-ASSISTED CONDITIONS", 《SYNTHETIC COMMUNICATIONS》 * |
| 王伯周等: "3,5-二氨基-1,2,4-三唑的合成与表征", 《化学试剂》 * |
| 贾思媛等: "3,5-二氨基-1,2,4 三唑硫酸盐的合成研究", 《精细化工中间体》 * |
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