CN101016268B - Chemical synthesis method for 2-formylcyanoacetylhydrazone-quinoxaline-1,4-dioxide - Google Patents
Chemical synthesis method for 2-formylcyanoacetylhydrazone-quinoxaline-1,4-dioxide Download PDFInfo
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- CN101016268B CN101016268B CN2007100513712A CN200710051371A CN101016268B CN 101016268 B CN101016268 B CN 101016268B CN 2007100513712 A CN2007100513712 A CN 2007100513712A CN 200710051371 A CN200710051371 A CN 200710051371A CN 101016268 B CN101016268 B CN 101016268B
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Abstract
The invention discloses a synthesizing method of 2-formyl cyano aceto hydrazone-quinoxaline-1, 4-dioxide, which comprises the following steps: adding benzofuran and acetone into reacting bottle; dripping pyrrolidone, diethylamine or condensed ammonia as catalyst slowly; refluxing; obtaining N, N-1, 4-dioxy-2-methyl quinoxaline as intermediate; adding the intermediate and selenium dioxide, manganese dioxide or chromium trioxide into reacting bottle; adding dimethyl sulfoxide and anhydrous alcohol; heating to obtain N, N-dioxy quinoxaline-2-formaldehyde as intermediate; adding cyanacethydrazide into the mass; stirring; adjusting pH value of reacting liquid; evolving product; filtering; drying; obtaining the product.
Description
Technical field
The invention belongs to technical field of medicine synthesis, be specifically related to a kind of 2-formylcyanoacetylhyd-azone-quinoxaline-1, the chemical synthesis process of 4-dioxide (the quinoline match is many).
Background technology
Mostly the quinoline match is that a kind of plan is developed as the compound of feed medicated premix, has antibiotic, growth promoting function.Its toxicity is little, and security is better than other similar medicine, has behind the animal-use drug to absorb soon, eliminates rapidly, and residual period is short, advantages such as no cumulative effect.Therefore study the concrete synthetic method of this fodder additives, have crucial economic benefit and social benefit.Only match many intermediates such as quinoxaline-N both at home and abroad at present about the chemosynthesis quinoline, N-1,4-titanium dioxide compound and N, N-1, the patent documentation report of 4-dioxy quinoxaline-2-formaldehyde and similar quinoxaline pharmaceutical methods does not still have patent and non-bibliographical information that how concrete, the complete operational path of synthetic quinoline match is studied.
United States Patent (USP) case in 1972 No. 3660398 (Kurt Ley, Leverknsen, Ulrich Eholzer etc., 1972; PatentSpecification 3660398) intermediate quinoxaline-N is disclosed, N-1, the synthetic method of 4-titanium dioxide compound has announced that with benzo furazan (BFO) be raw material, by the Beirut condensation reaction, generates multiple quinoxaline-N, N-1,4-titanium dioxide compound.Its reaction path is as follows:
English Patent case in 1967 No. 1058047 (Patent Specification 1058047) discloses intermediate N, N-1, the synthetic method of 4-dioxy quinoxaline-2-formaldehyde, promptly with 2-methyl-quinoxaline-N, N-1,4-dioxide are the synthetic N of raw material, N-1,4-dioxy quinoxaline-2-formaldehyde, and the synthetic on this basis carbadox that obtains.Synthetic according to following approach:
(PIETRO GARGANI and LUIGI PATTI, 1979 such as PIETRO GARGANI in 1979 and LUIGI PATTI; Patent Specification 1554819) on the basis of above patent, further improved synthesis step.They are obtaining 2-methyl-N, and N-1 on the basis of 4-dioxy quinoxaline, has synthesized carbadox by following steps.Concrete steps are as follows:
But the relevant quinoline of above patent or non-patent literature is matched many intermediated chemistries synthetic method reagent and is cost an arm and a leg, and reaction yield is low, and its synthesis technique needs to optimize.
Summary of the invention
The object of the invention is at still haveing nothing to do both at home and abroad in how concrete, the complete chemical synthesis process of quinoline match, propose a kind of economic and practical quinoline match polyvoltine synthesis route, improve that the synthetic intermediate route that has now in the document is unreasonable, cost is too high, can't implement the shortcoming of suitability for industrialized production.
The present invention is achieved through the following technical solutions:
1) be that the ratio of 40.6g: 60mL～90mL joins in the reaction flask with benzo furazan and acetone in mass volume ratio, under 45～75 ℃ of conditions, slowly drip the Pyrrolidine of 1.5mL～2.0mL or diethylamine or ammoniacal liquor respectively and make catalyzer, reflux, obtain N, N-1,4-dioxy-2-methyl-quinoxaline;
2) with N, N-1,4-dioxy-2-methyl-quinoxaline and tin anhydride or Manganse Dioxide or chromium trioxide are to join in the reaction flask in 1.0: 1.5～1.0: 2.0 by the amount of substance ratio, be 100: 5～15 adding dimethyl sulfoxide (DMSO) and dehydrated alcohols more by volume, be heated to 50～85 ℃, 5～9 hours reaction times obtained N, N-dioxy quinoxaline-2-formaldehyde;
3) with neohydrazid and N, N-dioxy quinoxaline-2-formaldehyde is to add in 1: 1～1: 3 in the mix products of above-mentioned steps preparation by the amount of substance ratio, at 10～30 ℃, reaction times is 2～10 hours, stirs conditioned reaction liquid pH to 4～8, treat that product separates out, filter, it is 2-formylcyanoacetylhyd-azone-quinoxaline-1 that oven dry obtains target product, the 4-dioxide.
Fodder additives 2-formylcyanoacetylhyd-azone-quinoxaline-1 involved in the present invention, the 4-dioxide has following basic structure (I):
(I)
Synthesis step is as follows:
1) intermediate N, N-1,4-dioxy-2-methyl-quinoxaline synthetic
As preferably: the mass volume ratio of benzo furazan and acetone is at 40.6g: between 60～90ml, catalyzer is selected Pyrrolidine or diethylamine, feeding intake of benzo furazan and catalyzer is 40.6g: 1.5ml～40.6g: 2.0ml, the volume ratio of catalyzer and acetone is 1: 8.6～1: 10, the rate of addition of catalyzer is about 24mL/ hour, and temperature of reaction is controlled between 50 ℃～70 ℃.
2) intermediate N, N-1,4-dioxy-quinoxaline-2-formaldehyde synthetic
As preferably: reaction solvent is that dimethyl sulfoxide (DMSO) (DMSO) is 100: 5～15 with the dehydrated alcohol volume ratio and is prepared to mixed solution, and catalyzer is selected tin anhydride, Manganse Dioxide, chromium trioxide (CrO
3/ (CH
3CO)
2O/H
2SO
4), and catalyzer and N, N-1,4-dioxy-2-methyl-quinoxaline amount of substance ratio is 1.5: 1.0～2.0: 1.0, and temperature is controlled between 60 ℃～70 ℃, the reaction times is 6～8 hours.
What 3) the quinoline match was many synthesizes
As preferably: with neohydrazid and step 2) in methyl-quinoxaline amount of substance ratio be 1: 1～1: 3, temperature of reaction is controlled at 20～28 ℃, between conditioned reaction system pH to 4～8, the reaction times is 3～8 hours.
Synthetic 2-formylcyanoacetylhyd-azone of the present invention-quinoxaline-1, the 4-dioxide can be used as feeding medicine, and its raw material is cheap and easy to get, the reaction conditions gentleness, production cost is low, and environmental pollution is little, and the product yield height is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is synthetic 2-formylcyanoacetylhyd-azone-quinoxaline-1, the 4-dioxide
1The H-NMR collection of illustrative plates
Fig. 2 is synthetic 2-formylcyanoacetylhyd-azone-quinoxaline-1, the 4-dioxide
13C-NMR figure
Fig. 3 is synthetic 2-formylcyanoacetylhyd-azone-quinoxaline-1,4-dioxide infrared spectrogram
Fig. 4 is synthetic 2-formylcyanoacetylhyd-azone-quinoxaline-1,4-dioxide ultraviolet spectrogram
Fig. 5 is synthetic 2-formylcyanoacetylhyd-azone-quinoxaline-1,4-dioxide mass spectrum
Embodiment
In the 4L four-hole boiling flask, drop into benzo furazan 40.6g, acetone 60mL, stirring makes it to dissolve fully, gets dark red solution.Slowly drip 1.5ml Pyrrolidine (using the 10mL acetone diluted) with dropping funnel under 45 ℃, in 30min, dropwise, stirred 2 hours.After finishing, reaction have a large amount of faint yellow solids to separate out, cooling, suction filtration, cleaning product, 70 ℃ of oven dry, yield 61.5%.
In the 4L four-hole boiling flask, add methyl-sulphoxide 100mL, dehydrated alcohol 5mL is heated to 50 ℃, adds the 0.15mol tin anhydride, stirs to make it to dissolve fully, adds the above-mentioned gained solid of 0.1mol then, continues reaction 5 hours.Room temperature is placed and is spent the night.Suction filtration gets red tan solution, directly mixed solution is used for next step reaction.
The dehydrated alcohol that adds 50mL in above-mentioned filtrate, dripping dilute sulphuric acid adjusting pH is 4.Slowly add the 0.1mol neohydrazid, can have precipitation to separate out, under 10 ℃ of conditions, continue reaction 2 hours then.Leave standstill, suction filtration, colourless to washing lotion with absolute ethanol washing, 70 ℃ of oven dry obtain end product 2-formylcyanoacetylhyd-azone-quinoxaline-1,4-dioxide (quinoline match many), yield 77.3%.
In the 4L four-hole boiling flask, drop into benzo furazan 40.6g, acetone 75mL, stirring makes it to dissolve fully, gets dark red solution.Slowly drip 1.75ml Pyrrolidine (using the 10mL acetone diluted) with dropping funnel under 60 ℃, in 30min, dropwise, stirred 2 hours.After finishing, reaction have a large amount of faint yellow solids to separate out, cooling, suction filtration, cleaning product, 70 ℃ of oven dry, yield 62.3%.
In the 4L four-hole boiling flask, add methyl-sulphoxide 100mL, dehydrated alcohol 10mL is heated to 65 ℃, adds the 0.4mol tin anhydride, stirs to make it to dissolve fully, adds the above-mentioned gained solid of 0.2mol then, continues reaction 7 hours.Room temperature is placed and is spent the night.Suction filtration gets red tan solution, directly mixed solution is used for next step reaction.
In above-mentioned reaction filtrate, add the dehydrated alcohol of 50mL, dripping 70% dilute sulphuric acid adjusting pH is 6.Slowly add the 0.1mol neohydrazid, can have precipitation to separate out, 20 ℃ are continued reaction 6 hours.Leave standstill, suction filtration, colourless to washing lotion with absolute ethanol washing, 70 ℃ of oven dry obtain end product 2-formylcyanoacetylhyd-azone-quinoxaline-1,4-dioxide (quinoline match many), yield 78.5%.
Embodiment 3
In the 4L four-hole boiling flask, drop into benzo furazan 40.6g, acetone 90mL, stirring makes it to dissolve fully, gets dark red solution.Slowly drip 2.0ml Pyrrolidine (using the 10mL acetone diluted) with dropping funnel under 75 ℃, in 30min, dropwise, continue to stir 2 hours.After finishing, reaction have a large amount of faint yellow solids to separate out, cooling, suction filtration, cleaning product, 70 ℃ of oven dry, yield 62.0%.
In the 4L four-hole boiling flask, add methyl-sulphoxide 100mL, dehydrated alcohol 15mL is heated to 85 ℃, adds the 0.6mol tin anhydride, stirs to make it to dissolve fully, adds the above-mentioned gained solid of 0.3mol then, continues reaction 9 hours.Room temperature is placed and is spent the night.Suction filtration gets red tan solution, directly mixed solution is used for next step reaction.
In above-mentioned reaction filtrate, add the dehydrated alcohol of 80mL, dripping sulfuric acid adjusting pH is 8.Slowly add the 0.1mol neohydrazid, can have precipitation to separate out, under 30 ℃ of conditions, continue reaction 10 hours then.Leave standstill, suction filtration, colourless to washing lotion with absolute ethanol washing, 70 ℃ of oven dry obtain end product 2-formylcyanoacetylhyd-azone-quinoxaline-1,4-dioxide (quinoline match many), yield 75.2%.
Embodiment 4
According to the synthesis step of embodiment 1, wherein the catalyzer Pyrrolidine is changed to diethylamine, must obtain end product 2-formylcyanoacetylhyd-azone-quinoxaline-1 at last, 4-dioxide (the quinoline match is many), yield 73.5%.
According to the synthesis step of embodiment 1, wherein the catalyzer Pyrrolidine is changed to ammoniacal liquor, must obtain end product 2-formylcyanoacetylhyd-azone-quinoxaline-1 at last, 4-dioxide (the quinoline match is many), yield 71.8%.
Embodiment 6
According to the synthesis step of embodiment 1, wherein the oxygenant tin anhydride is changed to Manganse Dioxide, must obtain end product 2-formylcyanoacetylhyd-azone-quinoxaline-1 at last, 4-dioxide (the quinoline match is many), yield 70.9%.
Embodiment 7
According to the synthesis step of embodiment 1, wherein the oxygenant tin anhydride is changed to chromium trioxide, must obtain end product 2-formylcyanoacetylhyd-azone-quinoxaline-1 at last, 4-dioxide (the quinoline match is many), yield 75.6%.
2-formylcyanoacetylhyd-azone-quinoxaline-1 that the present invention prepares, the 4-dioxide is as follows through ultraviolet, infrared, nucleus magnetic resonance, mass spectrum and ultimate analysis detected result:
1The H-NMR collection of illustrative plates: 4.413ppm is 15-CH among the figure
2 1The H displacement, 7.759-7.992ppm is 6,7 hydrogen
1The H displacement, 8.458-8.499ppm is 5,8 hydrogen
1The H displacement, 8.539ppm is 11 hydrogen
1The H displacement, 9.040ppm is 3 hydrogen
1The H displacement, 12.337ppm is 13-NH's
1The H displacement.(annotate: internal standard substance matter tetramethylsilane
1The H displacement is 0.00PPm, the solvent deuterated dimethyl sulfoxide
1The displacement of H is 2.499ppm, H in the solvent
2O's
1The H displacement is 3.317ppm), see Fig. 1.
13C-NMR figure: 24.350ppm is 15-CH among the figure
2 13The C displacement, 115.889ppm is 16-CN's
13C moves, and 119.777-119.960ppm is 6,7 C's
13The C displacement, 127.538ppm is 11 C's
13The C displacement, 132.080-132.365ppm is 5,8 C's
13The C displacement, 133.559ppm is 3 C's
13C displacement 137.128-137.576ppm is 9,10 C's
13The C displacement, 137.823ppm is 2 C's
13The C displacement, 165.759pp is 14-C=O's
13The C displacement.(annotate: the solvent deuterated dimethyl sulfoxide
13The displacement of C is 38.873-40.123ppm), see Fig. 2
Infrared spectrogram: 3454cm among the figure
-1For-NH-; 3147cm
-1For-CH=N-N; 2261cm
-1For-C ≡ N; 1694cm
-1For-C=O; 1507cm
-1Be phenyl ring; 732cm
-1Be quinoxaline ring, see Fig. 3.
Ultraviolet spectrogram: among the figure 238,306 and the 374nm place tangible absorption peak is arranged, the high conjugated system that presents quinoxaline ring has the K absorption band and the B absorption band of phenyl ring, sees Fig. 4.
Mass spectrum: m/z 270.1 is M-1 among the figure
1+, the molecular weight many with the quinoline match conform to; M/z 203.2 sloughs the fragment peak of cyanato for compound; M/z 175.3 is a quinoxaline-1, the fragment peak of 4-dioxy-2-methylene radical; M/z 171.0 is the fragment peak of quinoxaline-4-oxygen-cyano group; M/z 146.3 is the fragment peak of quinoxaline-4-oxygen.(solvent is a methyl alcohol; Ionization process adopts fast atom bombardment(FAB) to see Fig. 5.
Synthetic 2-formylcyanoacetylhyd-azone-quinoxaline-1 of the present invention, 4-dioxide results of elemental analyses is as shown in table 1, and (molecule is: C
12H
9N
5O
3).
Table 1 synthetic 2-of the present invention formylcyanoacetylhyd-azone-quinoxaline-1, the ultimate analysis of 4-dioxide
Claims (5)
1. 2-formylcyanoacetylhyd-azone-quinoxaline-1, the chemical synthesis process of 4-dioxide, its feature comprises following rapid:
1) be that the ratio of 40.6g: 60mL～90mL joins in the reaction flask with benzo furazan and acetone in mass volume ratio, slowly drip the Pyrrolidine of 1.5mL～2.0mL or diethylamine or ammoniacal liquor under 45～75 ℃ of conditions respectively and make catalyzer, backflow obtains N, N-1,4-dioxy-2-methyl-quinoxaline;
2) with N, N-1,4-dioxy-2-methyl-quinoxaline and tin anhydride or Manganse Dioxide or chromium trioxide join in the reaction flask than 1.0: 1.5～1.0: 2.0 by amount of substance, be 100: 5～15 adding dimethyl sulfoxide (DMSO) and dehydrated alcohols more by volume, add to 50～85 ℃, 5～9 hours reaction times obtained N, N-dioxy quinoxaline-2-formaldehyde;
3) with neohydrazid and N, N-dioxy quinoxaline-2-formaldehyde is that 1: 1～1: 3 adding above-mentioned steps prepares in the mix products by the amount of substance ratio, at 10～30 ℃, reaction times is 2～10 hours, stirs conditioned reaction liquid pH to 4～8, wait to produce and separate out, filter, it is 2-formylcyanoacetylhyd-azone-quinoxaline-1 that oven dry obtains target product, the 4-dioxide.
2. synthetic method according to claim 1, wherein the catalyzer of step 1) is diethylamine or Pyrrolidine.
3. synthetic method according to claim 1, wherein the temperature of reaction of step 1) is 50 ℃～70 ℃.
4. synthetic method according to claim 1, wherein step 2) temperature of reaction be 60 ℃～70 ℃, between reaction 6～8 hours.
5. synthetic method according to claim 1, wherein the temperature of reaction of step 3) is 20 ℃～28 ℃, is 3-8 hour between reaction.
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| CN102336768A (en) * | 2011-10-24 | 2012-02-01 | 中国科学院上海有机化学研究所 | N'-arylmethylene-2-(4-oxothiophene[2,3-d]pyrimidin-3-yl)acetyl hydrazone compounds, and preparation method and application thereof |
| CN103073511A (en) * | 2013-02-04 | 2013-05-01 | 中国农业大学 | Synthesis method for 2-formylcarbonylhydrazone-sulfaquinoxaline-N1, N4-dioxide |
| CN103224470A (en) * | 2013-05-17 | 2013-07-31 | 南京农业大学 | Preparation method and application of quinoxaline-6-phenylhydrazone derivants |
| CN103420930A (en) * | 2013-06-07 | 2013-12-04 | 华中农业大学 | Chemical synthetic method of cyadox |
| CN109535086B (en) * | 2019-01-29 | 2020-05-05 | 湖南科技学院 | Synthetic method of quinoxaline-2 (1H) -ketone C-3 carboxylate compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225604A (en) * | 1977-08-02 | 1980-09-30 | Spofa, Spojene Podniky Prop Farmaceutickou Vyrobu | 2-Formylquinoxaline-1,4-dioxide cyanoacetylhydrazone and methods for preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225604A (en) * | 1977-08-02 | 1980-09-30 | Spofa, Spojene Podniky Prop Farmaceutickou Vyrobu | 2-Formylquinoxaline-1,4-dioxide cyanoacetylhydrazone and methods for preparation thereof |
Non-Patent Citations (6)
| Title |
|---|
| 何进 |
| 李健洪 |
| 江洪.几种二氮氧化喹恶啉甲醛新衍生物的合成及其抑菌活性的研究.华中农业大学学报21 1.2002,21(1),91-94. |
| 游红 |
| 马敬中 |
| 马敬中;李健洪;游红;何进;江洪.几种二氮氧化喹恶啉甲醛新衍生物的合成及其抑菌活性的研究.华中农业大学学报21 1.2002,21(1),91-94. * |
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