CN103980256B - A kind of preparation method of dinitrogen oxyradical and structural characterization - Google Patents
A kind of preparation method of dinitrogen oxyradical and structural characterization Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and structural characterization of triazole dinitrogen oxyradical.Triazole dinitrogen oxyradical [3,5-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1<i>H</iGreatT.G reaT.GT-1,2,4-triazole] structural formula as follows:
the synthetic route of this imino nitroxide biradical introduced herein has synthesis step simply, processing ease, productive rate high.In addition, this compound is a kind of dinitrogen oxyradical with potential using value, and it shows strong ferromagnetic interaction under cryogenic, likely becomes new magneticsubstance and is used in the storing device aspect preparing computer.
Description
The present invention obtains the subsidy of state natural sciences fund (21371133) and Tianjin Natural Science Fund In The Light (12JCZDJC27600).
Technical field
The present invention relates to the preparation of dinitrogen oxyradical, particularly a kind of 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
h-1,2,4-triazole and preparation method and application.
Background technology
Molecular magnetic materials is owing to having the incomparable superiority of many traditional magnetic material, as high in information storage amount, magnetic loss-rate is little, it is shaping etc. to be easy to, and therefore its research is one of research field enlivened the most in recent years.Molecule ferro-magnetic refers to that (Tc) at a certain temperature utilizing chemical process to synthesize has the compound of picture magnet uniform quality.Wherein, nitroxyl free radical-metal complexes occupies an important position in the research of molecule based magnetic materials as an important system of molecular magnetism.
Ullman type nitroxyl free radical refers to the organic free radical containing N-O group, it is a part with paramagnetic center, have two can with the Sauerstoffatom of metal-complexing, the title complex obtained after itself and paramagnetic metallic ion coordination may demonstrate magnetic and light, the uncommon character that magnetic is associated with electricity etc.It is relatively simple that Ullman type nitroxyl free radical has synthesis, easily carries out chemically modified, metastable feature under room temperature and polarity condition.Italian Gatteschi in 1989 etc. obtain the title complex of nitroxyl free radical-metal first, and experiment proves that this title complex is molecule ferro-magnetic [A.Caneschi etc., Inorg.Chem., 1989,28,2940].In order to obtain higher-dimension structure, improve Tc temperature, after the mid-90 in 20th century, scientist starts the route of synthesis exploring new free radical-metal complexes, by designing and preparing the many dentates free radical that there is more coordinate base orders and there is suitable ligating atom, thus likely obtain the metal complexes with higher phase transition temperature.Wherein important method is a synthesis polyradical, and it has multiple NO group, more easily forms higher-dimension system with metallic ion coordination; Second method is the free radical of complex functionality, in free radical, namely introduces conjugation coordinating group as pyridine, imidazoles, triazole etc.The research of polyradical-metallic molecule magnet starts from 1993, D.Gatteschi study group diradical and Cu (II) synthesized there is ferromagnetic coupling title complex [A.Caneschi etc.,
inorg.Chem., 1993,32,1445].And the most outstanding surely belong to Japanese Iwamura study group [H.Iwamura etc.,
j.Am.Chem.Soc., 1996,118,1803], they reported the title complex of the three-dimensional structure that has three free radical bridging manganese metals to be formed in 1996, be the compound that in the free radical title complex reported at present, Tc temperature is the highest.P.Rey study group [P.Rey etc.,
angew.Chem.Int.Ed.Engl.1998,37,1270] title complex { Mn reported
2(NITI
m)
3clO
4crystalline structure show free radical oxygen and conjugation group imidazoles nitrogen all participate in coordination formed two dimension honeycomb-like network structure, such title complex ferromagnetic ordering temperature can reach T
cabout=40K.
Summary of the invention
The object of the invention is to be directed to above-mentioned analysis, a kind of 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1 is provided
h-1,2,4-triazole and preparation method, it is a kind of dinitrogen oxyradical based on triazole ring with potential using value, and have synthesis step few, operation is simple, the feature that productive rate is relatively high.
For this reason, the invention discloses following technical scheme:
The object of the invention is to disclose a kind of 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe synthetic method of-1,2,4-triazole;
3,5-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1 provided by the invention
hthe structural formula of-1,2,4-triazole:
The present invention can be write as: 3,5-
bis-Nit-Trz, Nit=4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical; Trz=1,2,4-triazole.
3,5-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1 provided by the invention
hthe preparation method of-1,2,4-triazole comprises the steps:
(1) 2, the synthesis of 2-dimethoxyacetic acid methyl esters: join in reaction flask by an a certain amount of glyoxylic acid and trimethyl orthoformate, stirs and oxoethanoic acid is all dissolved, then add the mixed solution of methyl alcohol and a small amount of vitriol oil, be heated to backflow, and keep backflow 18h.Cool to room temperature, extremely neutral with the methanol solution neutralization reaction liquid of sodium methylate, rotary evaporation removes excessive methyl alcohol, obtains the thick product of weak yellow liquid, then water pump underpressure distillation, obtains product 2,2-dimethoxyacetic acid methyl esters; Wherein the mixed solution of methyl alcohol and the vitriol oil refers to the mixed solution of 50ml methyl alcohol and 5 vitriol oil compositions;
(2) amino-3, the 5-dimethoxy methyl-4 of 4-
h-1, the synthesis of 2,4-triazole: after 2,2-dimethoxyacetic acid methyl esters and the mixing of a certain amount of hydrazine hydrate, 5h is reacted at 100 ° of C, then reaction system is slowly warming up to 160 ° of C, and keeps continuing reaction 10h at this temperature, be cooled to room temperature, adopt column chromatography to thick purifying products, leacheate ethyl acetate used: sherwood oil=4:1, obtains amino-3, the 5-dimethoxy methyl-4 of product 4-
h-1,2,4-triazole;
(3) 3,5-dimethoxy methyl isophthalic acids
hthe synthesis of-1,2,4-triazole: by amino for 4--3,5-dimethoxy methyl-4
h-1,2,4-triazole is dissolved in the hydrochloric acid of 5M, under 0 ~ 5 ° of C, then slowly drip the aqueous solution of Sodium Nitrite, dropwises rear continuation and stirs 2h, then repeatedly extract with chloroform, merge organic phase, filter and revolve desolventizing, obtain product 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole;
(4) 2, 3-dimethyl-2, the synthesis of 3-dihydroxyl butane vitriol: ammonium chloride is dissolved in ethanol-water mixed solvent, 2 are added under ice-water bath condition, 3-dinitrobenzene-2, 3-dimethylbutane, stir half hour, then add a certain amount of zinc powder in batches, after stirring half hour, remove ice-water bath, reaction 2h is continued under normal temperature, suction filtration, collect filtrate, a certain amount of dehydrated alcohol is added in filtrate, under ice-water bath, instill the ethanolic soln of 20% sulfuric acid, and stir half an hour, adularescent solid is separated out, filter, obtain product 2, 3-dimethyl-2, 3-dihydroxyl butane vitriol,
Wherein said ethanol-water mixed solvent refers to ethanol: the volume ratio 3:2 ethanolic soln of water;
Ammonium chloride and 2,3-dinitrobenzene-2,3-dimethylbutane mol ratio are 0.06mol:0.03mo;
(5) 3,5-, bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl tetrahydroglyoxalines)-1
hthe synthesis of-1,2,4-triazole: by 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole and Pinacol vitriol are dissolved in a certain amount of water, and under nitrogen protection, normal-temperature reaction 60h, filters, and collects filtrate, uses a certain amount of NaHCO
3solution neutralizes, and continues at ambient temperature to stir 6h, creates white solid, filter, with a small amount of water and washed with diethylether, can obtain product 3,5-bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl tetrahydroglyoxaline)-1 in reaction process
h-1,2,4-triazole;
(6) 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe synthesis of-1,2,4-triazole: by a certain amount of 3,5-bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl tetrahydroglyoxaline)-1
h-1,2,4-triazole is dissolved in chloroform, the lower aqueous solution slowly dripping sodium periodate of cryosel bath, and maintain the temperature at 5 ° of below C, continue reaction 20 minutes, separatory, collect organic phase, the desolventizing of decompression backspin, obtains violet solid 3,5-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
h-1,2,4-triazole.The mol ratio of wherein said 3,5-bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl tetrahydroglyoxaline)-1H-1,2,4-triazole and the sodium periodate aqueous solution is 2.6mmol:5.2mmol.
Wherein the mol ratio of the oxoethanoic acid described in step (1) and trimethyl orthoformate is 1:2.5 ~ 3;
2,2-dimethoxyacetic acid methyl esters wherein described in step (2) and the mol ratio of hydrazine hydrate are 1:2 ~ 3;
Amino-3, the 5-dimethoxy methyl-4 of 4-described in step (3)
hthe mol ratio 1:1.3 of-1,2,4-triazole and Sodium Nitrite; Amino-3, the 5-dimethoxy methyl-4 of 4-
hthe mol ratio of-1,2,4-triazole and hydrochloric acid is 1:2.5 ~ 3; The hydrochloric acid used in reaction is 5 mol/L; The concentration of the Sodium Nitrite used in reaction is 1 ~ 3.5 mol/L;
3,5-dimethoxy methyl isophthalic acids described in step (5)
h-1,2,4-triazole and Pinacol vitriol mol ratio are 1:2 ~ 2.5; 3,5-dimethoxy methyl isophthalic acids in reaction
hthe volumetric molar concentration of-1,2,4-triazole is 0.32 mol/L; Temperature of reaction is 25 ~ 70 ° of C; In and time use alkali be respectively 10% NaHCO
3solution, solid NaHCO
3, 10%KOH solution;
The present invention further discloses triazole dinitrogen oxyradical and prepare magneticsubstance for the application in computer memory device.3,5-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1 disclosed by the invention
h-1,2,4-triazole compounds is a kind of triazole species dinitrogen oxyradical with potential using value, and it is simple that this dinitrogen oxyradical has synthesis step, processing ease, the feature that productive rate is higher.
The present invention further discloses the magnetic characteristic of dinitrogen oxyradical, there is strong ferromagnetic interaction at low temperatures between free radical and free radical, itself likely becomes the molecular-based magnets of better performances.Molecule based magnetic materials has the incomparable superiority of many traditional magnetic material, as high in information storage amount, and magnetic loss-rate is little, it is shaping etc. to be easy to.Molecular-based magnets, for the preparation of computer memory device, can not only improve the arithmetic speed of computer, and greatly can improve the store content of computer, in computer miniaturization, has potential using value.
Accompanying drawing explanation
Fig. 1 is compound 3,5-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe electron paramagnetic resonance schematic diagram of-1,2,4-triazole;
Fig. 2 is 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe infrared spectrum of-1,2,4-triazole;
Fig. 3 is 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe molar susceptibility of-1,2,4-triazole and the product variation with temperature graphic representation of temperature;
Fig. 4 is 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe structural formula of-1,2,4-triazole.
Embodiment
Below in conjunction with embodiment, the present invention is further described, and following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.Various raw material of the present invention all has commercially available.
Embodiment 1
3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe chemical formula of-1,2,4-triazole is: 3,5-
bis-Nit-Trz, its preparation process is as follows:
(1) 2,2-dimethoxyacetic acid methyl esters (
i) synthesis:
The trimethyl orthoformate of 15g (0.16mol) glyoxylic acid and 52ml (0.48mmol) is joined in the there-necked flask of 250ml, stirring makes oxoethanoic acid all dissolve, then add 50ml methyl alcohol and 5 vitriol oils, be heated to backflow, and keep backflow 18h.Cool to room temperature, with the methanol solution neutralization reaction liquid of sodium methylate to PH=7, rotary evaporation removes excessive methyl alcohol, obtains the thick product of weak yellow liquid, then water pump underpressure distillation, obtain product 2,2-dimethoxyacetic acid methyl esters (
i) 12.55g, productive rate: 59.8%, product boiling point: 67-69 ° C/18mmHg.In reaction, the mol ratio of oxoethanoic acid and trimethyl orthoformate is 1:3.
Reaction formula:
(2) amino-3, the 5-dimethoxy methyl-4 of 4-
h-1,2,4-triazole (
iI) synthesis
By 12.55g (0.094mol) 2,2-dimethoxyacetic acid methyl esters and 12g (0.24mol) hydrazine hydrate are mixed in 100ml round-bottomed flask, then 100 ° of C are heated to, and remain on 100 ° of C reaction 5h, in 4h, temperature is slowly heated to 160 ° of C(risings per hour, 15 ° of C afterwards) remove excessive hydrazine hydrate and react the water produced, and remain on 160 ° of C reaction 10h, cooled post (adopt the volume ratio of leacheate to be ethyl acetate: sherwood oil=4:1), obtain amino-3, the 5-dimethoxy methyl-4 of product 4-
h-1,2,4-triazole (II) 9.8g, productive rate is 45%.Fusing point: 71-74 ° C.In reaction, the mol ratio of dimethoxyacetic acid methyl esters and hydrazine hydrate is 1:2.5;
Reaction formula:
(3) 3,5-dimethoxy methyl isophthalic acids
h-1,2,4-triazole (
iII)
0.75g Sodium Nitrite (10.9mmol) is dissolved in the water of 3ml, by amino for 4--3,5-dimethoxy methyl-4
h-1,2,4-triazole 1.99g (8.6mmol) (
iI) be dissolved in the hydrochloric acid soln of the 5M of 5.45ml, the aqueous solution of Sodium Nitrite is slowly added drop-wise in the solution of (II) under the condition of ice-water bath, and keep reacting liquid temperature at 0 ~ 5 ° of C, dropwise rear continuation and stir 2h, then repeatedly extract (5 × 30ml) with chloroform, merge organic phase, use a small amount of anhydrous magnesium sulfate drying, desolventizing is revolved in filtration, obtains product 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole (III) 1.25g, productive rate 69.06%, fusing point 96-100 ° C.In reaction, the mol ratio of Compound II per and Sodium Nitrite is 1:1.3, and in reaction, the mol ratio of Compound II per and hydrochloric acid is 1:2.5, and the concentration of reaction Sodium Nitrite is 3.5 mol/L;
Reaction formula:
(4) Pinacol vitriol (
iV) synthesis
3.25g (0.06mol) ammonium chloride is dissolved in alcohol-water (3:2) solution of 55ml, 5.2g (0.03mol) 2 is added under ice-water bath condition, 3-dinitrobenzene-2, 3-dimethylbutane, stir half hour, then add the zinc powder of 13g (0.2mol) in batches, after stirring half hour, remove ice-water bath, reaction 2h is continued under normal temperature, suction filtration, with 30mL95% washing with alcohol solid, collect filtrate, 112ml dehydrated alcohol is added in filtrate, under ice-water bath, the ethanolic soln of instillation 8ml20% sulfuric acid, and stir half an hour, suction filtration, product IV 4g can be obtained, productive rate is 55%.Fusing point: 172-174 ° C.
Reaction formula:
(5) 3,5-, bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl tetrahydroglyoxalines)-1
hthe synthesis of-1,2,4-triazole (
v)
By 1g (6.5mmol) 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole (III) and 3.44g (13.9mmol) 2,3-dimethyl-2; 3-dihydroxyl butane vitriol (IV) is dissolved in 20ml water, and under nitrogen protection, normal-temperature reaction 60h, filters; removing impurity, collects filtrate, with the solid NaHCO of 2.34g (27.9mmol)
3be dissolved in the solution neutralization of (21ml water), and continue at ambient temperature to stir 6h, create white solid in reaction process, filter, respectively wash twice with a small amount of water and ether, product 3,5-bis--(4,4 can be obtained, 5,5-tetramethyl--1,3-dihydroxyl tetrahydroglyoxaline)-1
hthe synthesis (V) of-1,2,4-triazole, productive rate is 45%.Nuclear magnetic data:
1hNMR (DMSO), 7.71 (s, 4H), 4.59 (s, 2H), 1.05 (s, 24H).(in reaction, the mol ratio of compound III and compound IV is 1:2.1, NaHCO
3the concentration of solution is 10%).
Reaction formula:
(6) 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe synthesis of-1,2,4-triazole (
vI)
By 1g (2.6mmol) 3,5-bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl tetrahydroglyoxaline)-1
h-1,2,4-triazole (V) is dissolved in the chloroform of 25ml, slowly drips 1.11g (5.2mmol) sodium periodate (NaIO under cryosel bath
4) be dissolved in the solution of 25ml water, dripped off in 40 minutes, and maintain the temperature at 5 ° of below C, continue reaction 20 minutes, separatory, collect organic phase, inorganic phase with 10ml chloroform extraction once, merge organic phase, by saturated common salt water washing organic phase, then use MgSO
4dry half hour, filter, the desolventizing of decompression backspin, obtain violet solid (VI) 0.42g, productive rate is 45%, product fusing point: 112-116 ° C.(mol ratio of compound V and sodium periodate is 1:2).
Reaction formula:
1) mensuration of ultimate analysis:
Ultimate analysis adopts on Perkin-Elmer elemental analyser and measures.
Elemental analysis data: C
16h
25n
7o
4(379.4): C, 50.27% (calc50.65%); H, 6.33% (calc6.64%); N, 25.63% (calc25.84%).
2) mensuration of electron paramagnetic resonance:
Electron paramagnetic resonance completes in BrukerEMX-6/1 type electron spin resonance spectrometer, and microwave frequency is 9.2GHz, power 200mW, and modulated magnetic field is 0.32mT.
Fig. 1 is 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe electron paramagnetic resonance schematic diagram of-1,2,4-triazole.Demonstrate diradical in figure five heavily split swarming.
3) mensuration of infrared spectrum:
Infrared spectra measures on Tensor27 infrared spectrometer, and instrumental resolution is 0.5 ~ 1cm
-1, adopt 24 DigiTectTM detector systems and ROCKSOLIDTM interferometer two patented technologies, adopt 24 high speed DeltaSigmaTM type A/D converters, Fast Fourier Transform (FFT).Solid sample KBr compressing tablet, at 4000 ~ 400cm
-1measure in scope.
Fig. 2 is 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe infrared spectrum of-1,2,4-triazole.1359.4cm in figure
-1show the N-O stretching vibration absorption peak of free radical.
4) molar susceptibility is specific:
Magnetic Test uses QuantumDesignMPMSXL-7SQUID device to complete.
Fig. 3 is the molar susceptibility of this triazole dinitrogen oxyradical and the product variation with temperature graphic representation of temperature.Show in figure: between free radical and free radical, have strong ferromagnetic interaction at low temperatures, likely become the molecular-based magnets of excellent performance.Molecular magnet, for the preparation of computer memory device, can not only improve the arithmetic speed of computer, and greatly can improve the store content of computer, in computer miniaturization, has potential using value.
Embodiment 2
The preparation method of dinitrogen oxyradical:
(1) 2,2-dimethoxyacetic acid methyl esters (
i) synthesis: trimethyl orthoformate in add a certain amount of oxoethanoic acid, stir oxoethanoic acid is all dissolved, then add methyl alcohol and the micro-vitriol oil, be heated to backflow, and keep backflow 18h.Cool to room temperature, with the methanol solution neutralization reaction liquid of sodium methylate to PH=7, rotary evaporation removes excessive methyl alcohol, obtains the thick product of weak yellow liquid, then water pump underpressure distillation, obtain product 2,2-dimethoxyacetic acid methyl esters (
i), described oxoethanoic acid and the mol ratio of trimethyl orthoformate are 1:2.5, and productive rate is 49%;
(2) amino-3, the 5-dimethoxy methyl-4 of 4-
h-1,2,4-triazole (
iI) synthesis: by 2,2-dimethoxyacetic acid methyl esters and hydrazine hydrate are mixed in reaction, then 100 ° of C are heated to, and remain on 100 ° of C reaction 5h, in 4h, temperature is slowly heated to 160 ° of C(risings per hour, 15 ° of C afterwards), and remain on 160 ° of C and react 10h, cooled post separate reacted mixture (adopt the volume ratio of leacheate to be ethyl acetate: sherwood oil=4:1), obtain amino-3, the 5-dimethoxy methyl-4 of product 4-
h-1,2,4-triazole.Described dimethoxyacetic acid methyl esters and the mol ratio of hydrazine hydrate are 1:1, and productive rate is 30%;
(3) 3,5-dimethoxy methyl isophthalic acids
h-1,2,4-triazole: the aqueous solution of Sodium Nitrite is slowly added dropwise to 4-amino-3,5-dimethoxy methyl-4
hin the hydrochloric acid soln of-1,2,4-triazole (II), and keep reacting liquid temperature at 0 ~ 5 ° of C, dropwise rear continuation and stir 2h, then use chloroform extraction, merge organic phase, use a small amount of anhydrous magnesium sulfate drying, desolventizing is revolved in filtration, obtains product 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole (III); Amino-3, the 5-dimethoxy methyl-4 of 4-in described reaction
h-1,2,4-triazole (II) is 1:1.3 with the mol ratio of Sodium Nitrite; Compound (II) is 1:2.5 with the mol ratio of hydrochloric acid; The hydrochloric acid used in reaction is 5 mol/L; The concentration of the Sodium Nitrite used in reaction is 2 mol/L; Productive rate is 52%;
(4) Pinacol vitriol (
iV) synthesis: a certain amount of ammonium chloride is dissolved in alcohol-water (3:2) mixing solutions, 2,3-dinitrobenzene-2,3-dimethylbutane is added under ice-water bath condition, stir half hour, then add zinc powder in batches, after stirring half hour, remove ice-water bath, reaction 2h is continued under normal temperature, suction filtration, uses washing with alcohol solid, collects filtrate, a small amount of dehydrated alcohol is added in filtrate, under ice-water bath, instill the ethanolic soln of 20% sulfuric acid, and stir half an hour, suction filtration, can obtain product Pinacol vitriol (
iV);
(5) 3,5-, bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl tetrahydroglyoxalines)-1
hthe synthesis of-1,2,4-triazole (
v): by 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole (III) and Pinacol vitriol (IV) are dissolved in water, and under nitrogen protection, room temperature reaction 60h, filters, and removing impurity, collects filtrate, use NaHCO
3solid neutralizes, and continues at ambient temperature to stir 6h, and create micro-white solid in reaction process, filter, can obtain product (V), productive rate is 10%.In reaction, the mol ratio of compound III and compound IV is 1:2;
(6) 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe synthesis of-1,2,4-triazole (
vI): by 3,5-, bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl tetrahydroglyoxaline)-1
h-1,2,4-triazole (V) is dissolved in chloroform, slowly drips sodium periodate (NaIO under cryosel bath
4) the aqueous solution, and maintain the temperature at 0 ~ 5 ° of C, continue reaction 20 minutes, separatory, collect organic phase, then use MgSO
4dry half hour, filter, the desolventizing of decompression backspin, obtain violet solid (VI), productive rate is 45%.The mol ratio of compound V and sodium periodate is 1:2.
Embodiment 3
The preparation method of dinitrogen oxyradical:
(1) 2,2-dimethoxyacetic acid methyl esters (
i) synthesis: trimethyl orthoformate in add a certain amount of oxoethanoic acid, stir oxoethanoic acid is all dissolved, then add methyl alcohol and the micro-vitriol oil, be heated to backflow, and keep backflow 24h.Cool to room temperature, with the methanol solution neutralization reaction liquid of sodium methylate to PH=7, rotary evaporation removes excessive methyl alcohol, obtains the thick product of weak yellow liquid, then water pump underpressure distillation, obtain product 2,2-dimethoxyacetic acid methyl esters (
i).Described oxoethanoic acid and the mol ratio of trimethyl orthoformate are 1:3, and productive rate is 60%;
(2) amino-3, the 5-dimethoxy methyl-4 of 4-
h-1,2,4-triazole (
iI) synthesis: by 2,2-dimethoxyacetic acid methyl esters and hydrazine hydrate are mixed in reaction, then 100 ° of C are heated to, and remain on 100 ° of C reaction 5h, in 4h, temperature is slowly heated to 160 ° of C(risings per hour, 15 ° of C afterwards), and remain on 160 ° of C and react 10h, cooled post separate reacted mixture (adopt the volume ratio of leacheate to be ethyl acetate: sherwood oil=4:1), obtain amino-3, the 5-dimethoxy methyl-4 of product 4-
h-1,2,4-triazole; Described dimethoxyacetic acid methyl esters and the mol ratio of hydrazine hydrate are 1:2; Productive rate is 40%;
(3) 3,5-dimethoxy methyl isophthalic acids
h-1,2,4-triazole: 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole: the aqueous solution of Sodium Nitrite is slowly added dropwise to 4-amino-3,5-dimethoxy methyl-4
hin the hydrochloric acid soln of-1,2,4-triazole (II), and keep reacting liquid temperature at 0 ~ 5 ° of C, dropwise rear continuation and stir 2h, then use chloroform extraction, merge organic phase, use a small amount of anhydrous magnesium sulfate drying, desolventizing is revolved in filtration, obtains product 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole (III).Amino-3, the 5-dimethoxy methyl-4 of 4-in described reaction
h-1,2,4-triazole (II) is 1:1.3 with the mol ratio of Sodium Nitrite, and compound (II) is 1:2.5 with the mol ratio of hydrochloric acid, and the hydrochloric acid used in reaction is 5 mol/L, and the concentration of the Sodium Nitrite used in reaction is 1 mol/L, and productive rate is 41%;
(4) Pinacol vitriol (
iV) synthesis: a certain amount of ammonium chloride is dissolved in alcohol-water (3:2) mixing solutions, 2,3-dinitrobenzene-2,3-dimethylbutane is added under ice-water bath condition, stir half hour, then add zinc powder in batches, after stirring half hour, remove ice-water bath, reaction 2h is continued under normal temperature, suction filtration, uses washing with alcohol solid, collects filtrate, a small amount of dehydrated alcohol is added in filtrate, under ice-water bath, instill the ethanolic soln of 20% sulfuric acid, and stir half an hour, suction filtration, can obtain product Pinacol vitriol (
iV);
(5) 3,5-, bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl tetrahydroglyoxalines)-1
hthe synthesis of-1,2,4-triazole (
v): by 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole (III) and 2; 3-dimethyl-2,3-dihydroxyl butane vitriol (IV) is dissolved in water, under nitrogen protection; 70 ° of reaction 10h, filter, removing impurity; collect filtrate; with the KOH solution neutralization of 10%, and continue at ambient temperature to stir 6h, in reaction process, create micro-white solid; filter, productive rate is 38%.In reaction, the mol ratio of compound III and compound IV is 1:2;
(6) 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe synthesis of-1,2,4-triazole (
vI): by 3,5-, bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl tetrahydroglyoxaline)-1
h-1,2,4-triazole (V) is dissolved in chloroform, slowly drips sodium periodate (NaIO under cryosel bath
4) the aqueous solution, and maintain the temperature at 0 ~ 5 ° of C, continue reaction 20 minutes, separatory, collect organic phase, then use MgSO
4dry half hour, filter, the desolventizing of decompression backspin, obtain violet solid (VI), productive rate is 45%.The mol ratio of compound V and sodium periodate is 1:2.
Claims (1)
1.3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe preparation method of-1,2,4-triazole, is characterized in that being undertaken by following step:
(1) 2, the synthesis of 2-dimethoxyacetic acid methyl esters: join in reaction flask by an a certain amount of glyoxylic acid and trimethyl orthoformate, stirs and oxoethanoic acid is all dissolved, then add the mixed solution of methyl alcohol and a small amount of vitriol oil, be heated to backflow, and keep backflow 18h;
Cool to room temperature, extremely neutral with the methanol solution neutralization reaction liquid of sodium methylate, rotary evaporation removes excessive methyl alcohol, obtains the thick product of weak yellow liquid, then water pump underpressure distillation, obtains product 2,2-dimethoxyacetic acid methyl esters; Wherein the mol ratio of oxoethanoic acid and trimethyl orthoformate is 1:2.5-3; The mixed solution of methyl alcohol and the vitriol oil refers to the mixed solution of 50ml methyl alcohol and 5 vitriol oil compositions;
(2) amino-3, the 5-dimethoxy methyl-4 of 4-
h-1, the synthesis of 2,4-triazole: after 2,2-dimethoxyacetic acid methyl esters and the mixing of a certain amount of hydrazine hydrate, at 100 DEG C of reaction 5h, then reaction system is slowly warming up to 160 DEG C, and keeps continuing reaction 10h at this temperature, be cooled to room temperature, adopt column chromatography to thick purifying products, leacheate solvent volume used is than ethyl acetate: sherwood oil=4:1, obtains amino-3, the 5-dimethoxy methyl-4 of product 4-
h-1,2,4-triazole; Wherein the mol ratio of 2,2-dimethoxyacetic acid methyl esters and hydrazine hydrate is 1:2-3;
(3) 3,5-dimethoxy methyl isophthalic acids
hthe synthesis of-1,2,4-triazole: by amino for 4--3,5-dimethoxy methyl-4
h-1,2,4-triazole is dissolved in the hydrochloric acid of 5M, at 0-5 DEG C, then slowly drip the aqueous solution of Sodium Nitrite, dropwises rear continuation and stirs 2h, then repeatedly extract with chloroform, merge organic phase, filter and revolve desolventizing, obtain product 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole; Wherein amino-3, the 5-dimethoxy methyl-4 of 4-
hthe mol ratio 1:1.3 of-1,2,4-triazole and Sodium Nitrite; Amino-3, the 5-dimethoxy methyl-4 of 4-
hthe mol ratio of-1,2,4-triazole and hydrochloric acid is 1:2.5; The hydrochloric acid used in reaction is 5 mol/L; The concentration of the Sodium Nitrite used in reaction is 1-3.5 mol/L;
(4) 2, 3-dimethyl-2, the synthesis of 3-dihydroxyl aminobutane vitriol: ammonium chloride is dissolved in ethanol-water mixed solvent, 2 are added under ice-water bath condition, 3-dinitrobenzene-2, 3-dimethylbutane, stir half hour, then add a certain amount of zinc powder in batches, after stirring half hour, remove ice-water bath, reaction 2h is continued under normal temperature, suction filtration, collect filtrate, a certain amount of dehydrated alcohol is added in filtrate, under ice-water bath, instill the ethanolic soln of 20% sulfuric acid, and stir half an hour, adularescent solid is separated out, filter, obtain product 2, 3-dimethyl-2, 3-dihydroxyl aminobutane vitriol, ethanol-water mixed solvent refers to ethanol: the volume ratio 3:2 ethanolic soln of water, ammonium chloride and 2,3-dinitrobenzene-2,3-dimethylbutane mol ratio are 0.06mol:0.03mol,
(5) 3,5-, bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl imidazolidines)-1
hthe synthesis of-1,2,4-triazole: by 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole and 2,3-dimethyl-2,3-dihydroxyl aminobutane vitriol are dissolved in a certain amount of water, and under nitrogen protection, normal-temperature reaction 60h, filters, and collects filtrate, uses a certain amount of NaHCO
3solution neutralizes, and continues at ambient temperature to stir 6h, creates white solid, filter, with a small amount of water and washed with diethylether, can obtain product 3,5-bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl imidazolidine)-1 in reaction process
h-1,2,4-triazole; 3,5-dimethoxy methyl isophthalic acid
h-1,2,4-triazole and 2,3-dimethyl-2,3-dihydroxyl aminobutane vitriol mol ratio are 1:2 ~ 2.5; 3,5-dimethoxy methyl isophthalic acids in reaction
hthe volumetric molar concentration of-1,2,4-triazole is 0.32 mol/L; In and time use alkali be the NaHCO of 10%
3solution;
(6) 3,5-, bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
hthe synthesis of-1,2,4-triazole: by a certain amount of 3,5-bis--(4,4,5,5-tetramethyl--1,3-dihydroxyl imidazolidine)-1
h-1,2,4-triazole is dissolved in chloroform, the lower aqueous solution slowly dripping sodium periodate of cryosel bath, and maintain the temperature at less than 5 DEG C, continue reaction 20 minutes, separatory, collect organic phase, the desolventizing of decompression backspin, obtains violet solid 3,5-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-is oxidized-1-oxygen base free radical)-1
h-1,2,4-triazole;
Its structure is as follows:
。
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