CN100532379C - Preparation process of quinamine alcohol - Google Patents
Preparation process of quinamine alcohol Download PDFInfo
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- CN100532379C CN100532379C CNB2007101235733A CN200710123573A CN100532379C CN 100532379 C CN100532379 C CN 100532379C CN B2007101235733 A CNB2007101235733 A CN B2007101235733A CN 200710123573 A CN200710123573 A CN 200710123573A CN 100532379 C CN100532379 C CN 100532379C
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Abstract
The present invention relates to chemical synthesis technology, and is especially preparation process of quinamine alcohol as one kind of quinoxaline compounds. Quinamine alcohol is one kind of animal medicine with high antibiotic effect and growth promoting effect but certain toxicity. During the preparation, acetyl methylquine material is made to produce condensation reaction, or Claisen-Schmidt reaction, with furaldehyde in the alkaline condition with ethylenediamine to produce alpha, beta-unsaturated ketone. The process in new synthesis path can obtain quinamine alcohol crystal with high antibiotic effect, high growth promoting effect and low toxicity.
Description
Technical field
The present invention relates to the field of chemical synthesis of organic compound, especially the quinoxaline compound is synthetic.
Background technology
Since the Haddalin of nineteen sixty-five Beirut,Lebanon (Beirut) and Issidorides deliver first piece of article of Beirut reaction, existing hundreds of used this reaction synthetic patent appearance and synthetic not next thousand kinds of new N, the N-diaza is-1,4 dioxide (quinoxaline how) compounds.In fact, according to the substitutive derivative of the multiple quinoxaline chemical combination of Beirut reaction synthetic material as: dysentery upright clear (Catbadox), olaquindox (Olaquindox), mequindox etc. are applied in animal and veterinary and the aquaculture as antibiotic and growth promoter, have obtained huge economy and society benefit.But there is bigger toxic side effect in this compounds, merely changes its side chain and can not satisfy the demand, because result's toxicity reduction often, its effect also descends greatly.
Must seek for this reason and a kind ofly have anti-microbial activity and growth promoting function height, but toxicity is far below the medicated feed additive new variety that development potentiality De quinoxaline is arranged of similar medicine.
The article source of beirut is: Haddadin M J, Issidorides C H.Benzofurazan Oxide, Reactions withEnolate Anions[J] .Tetrahedron lett.1965,3253.
Summary of the invention
Purpose of the present invention is for providing a kind of anti-microbial activity and growth promoting function strong, but the preparation method of the low quinamine alcohol of toxicity.
Quinamine alcohol is to be raw material with the mequindox, be reflected at the carbonyl generation condensation reaction of α one hydrogen atom and the furtural of mequindox under the diethylamine alkaline condition by Claisen-schmidt, and dehydration gets α, beta unsaturated ketone.Synthetic route is:
Processing step is as follows:
(1) 18.3g o-Nitraniline and 0.42g Tetrabutyl amonium bromide are dissolved in the 70g toluene, 50% aqueous sodium hydroxide solution that adds 25.3g, stir down at 15-20 ℃, splash into the 127g aqueous sodium hypochlorite solution, continue down to stir at 15-20 ℃ then, divide the phase of anhydrating, get the toluene solution of benzo furazan-1-oxide compound, under vacuum, boil off toluene, get benzo furazan-1-oxide compound of 17.4g.
(2) the benzo furazan-1-oxide compound of 16.2g and the methyl ethyl diketone of 13.5g are dissolved in the triethylamine of 30ml, allow this solution at room temperature leave standstill, collecting precipitation can get 2-ethanoyl-2 Jia based quinoxaline-1,4 dioxide after the drying.
2-ethanoyl-2 Jia based quinoxaline-1 with 5g; 4 dioxide are dissolved in the furtural of 10g, are heated to dissolving, are placed on to be cooled to 20-35 ℃ in the mixture of ice and water; slowly pour the 4ml diethylamine into; color gradually becomes brown, in entry, continues to stir; there is precipitation to separate out; suction filtration obtains thick product, and ethyl alcohol recrystallization obtains the pure product of quinamine alcohol.
It is Powdered that compound of the present invention is yellow solid, with the method that spectroscopy is identified this material carried out the chemical structure test.
Spectroscopy is identified:
1, infrared spectra (IR): instrument adopts Nicolet NEXUS 670 FT-IR instruments, IR (KBr) cm
-1: 3500-2846,3103,1668,1604,1546,1316,1335,1271,758;
2, mass spectrum (NS): instrument model: ZAB-HS, FAB-MS show [M]
+296;
3, nucleus magnetic resonance (NMR) instrument adopts the INOVA-400MHz NMR spectrometer with superconducting magnet,
1HNMR (CDCL
3) δ ppm:8.61 (1H, d, J=8.4Hz, H-5), 8.55 (1H, d, J=8.4Hz, H-8), 7.85 (2H, m, H-6, H-7), 7.53 (1H, H-16), 7.34 (1H, d, J=15.6Hz, H-13), 6.96 (1H, d, J=15.6Hz, H-12), 6.75 (1H, d, J=3.6Hz, H-18), 6.49 (1H, d, J=2.0,3.6Hz, H-17), 2.53 (3H, s, 3-CH
3);
13CNMR (CDCL
3) δ ppm; 185.2,150.4,146.4,139.9,139.1,137.8,136.9,132.7,132.5,131.4,121.9,120.2,120.1,118.5,113.2,14.2; According to the FAB-MS data, syncaryon mr (NMR) spectrum data can determine that this compound molecule formula is C
16H
12N
2O
4, molecular weight is 296; According to the proton signal on the HMQC ownership carbon, belong to hydrocarbon long-range relevantly according to HMBC, COSY shows that the proton on 5,8 has the long-range coupling relation with 6,7 proton, and the proton on 12 and 13 has long-range even Yu to concern, proton on 17 and 16,18 has the long-range coupling relation;
Above data and analytical results can determine that this compound is a quinamine alcohol.
Table 1: compound
1HNMR (400MHz) and
13CNMR (100MHz) data and gHMBC mutual relationship (δ, ppm, TMS, CDCl
3)
Draw following molecular structure according to above test,
Through inspection information, before our research, all there is not the medicated feed additive of this class formation both at home and abroad, though identical female ring structure is arranged, the side chain difference, so the present invention is a kind of innovation aspect molecular structure.
The productive rate 60-90% of building-up reactions obtains quinamine alcohol crystallization purity and reaches more than 98%.
Because consumption concept and people are to the healthy concern of oneself, synthetic antibiotic evaluation is become very important, for estimating and promoting the use of quinamine alcohol, also, quinamine alcohol promotes growth test, toxicity test and drug residue analysis have been done for the food sanitation aspect provides a theoretical foundation.
One gaining effect and the research of promotion protein assimilation
1. the comparison of several synthetic antibiotic additive growth promoting functions
1.1 on August 7th, 2003 was advanced 400 of 1 age in days peace carminum plumage chick from magnificent Gansu Province kind chicken house in the grouping of examination chicken, according to random packet, the principle of male and female half and half is divided into 5 groups, initial body weight difference is not remarkable between group, is divided into 4 repetitions in the group again, accepts blank respectively, olaquindox (50ppm), quinamine alcohol (50ppm), quinamine alcohol (100ppm), five processing of Quinocetone (50ppm).
1.2 raise the complete feed and the experimental drug thing additive of feeding and preparing voluntarily since 1 age in days, free choice feeding is freely drunk water.Write down food consumption every day, weigh weekly and remain the material amount, and carry out immunity by raising handbook.
, draw the olaquindox group by statistics and improve 3.5% than control group day weight gain behind 42 ages in days 1.3 conclusion is fed, food consumption improves 5.4%; Quinamine alcohol (50ppm) group improves 8.3% than control group day weight gain, and food consumption improves 7.2%; Quinocetone (50ppm) group improves 8.00% than control group day weight gain, and food consumption improves 7.29%.When quinamine alcohol (100ppm) is organized 42 ages in days and control group more not remarkable than difference.Quinamine alcohol (50ppm) compares gaining effect with Quinocetone (50ppm) group and food consumption difference is not remarkable.
2. gaining effect and protein stimulatory are relatively synthetic between the quinamine alcohol different concns gradient
2.1 grouping and raise on September 28th, 2003 and advance 200 of 1 age in days peace carminum plumage chick from magnificent Gansu Province kind chicken house, feed after the week, according to random packet, the principle of male and female half and half is divided into 4 groups, grouping is after check body weight difference is not remarkable, and every group is divided into 4 repetitions again.Accept blank respectively for 4 groups, quinamine alcohol (50ppm), quinamine alcohol (75ppm), quinamine alcohol (100ppm), 4 processing.Raise whole process and do not add other microbiotic, method for breeding is identical with first experiment.Write down charging capacity every day, claim examination chicken body weight and clout amount weekly.Raising experiment is to end of day in November 24, totally 56 days.
2.2 conclusion is added 50ppm quinamine alcohol food consumption by statistics and day weight gain improves 7.28% and 8.93% than control group respectively; 75ppm quinamine alcohol group improves 4.4% and 4.97% than control group food consumption and day weight gain; And 100ppm quinamine alcohol group and control group ratio have raising slightly, but difference is not remarkable.Therefore, interpolation 50ppm quinamine alcohol gaining effect is more satisfactory in the daily ration of chicken.
Two quinamine alcohols are in the intravital drug residue analysis of chicken
1 detects the wavelength quinamine alcohol ultraviolet absorption value, detects 3 wavelength 334nm of high absorption peak on ultraviolet-visible spectrophotometer, 254nm, and 228nm, it is more satisfactory to detect the 334nm wavelength ratio through high performance liquid phase.
2 moving phase moving phase ranges of choice are bigger, when the kind of change moving phase and ratio, all can imitate by coupled columns, and separating effect produces big influence.Therefore, we do a lot of work when selecting moving phase, have selected acetonitrile according to polarity and solvability, and the first alcohol and water is done moving phase, and acetonitrile and methyl alcohol retention time are 3.16 minutes, and acetonitrile and water are 7.32 minutes, so moving phase is decided to be water and acetonitrile.After testing quinamine alcohol in this moving phase 100ng-800ng in linearity range.
3 sample preparations accurately take by weighing 2g tissue, add the homogenate 5 minutes on FSH-2 of 4ml acetonitrile, accurately even get be equivalent to the 1g tissue homogenate in 10ml tool plug centrifuge tube, add 1ml saturated ammonium sulphate vibration 20 minutes, centrifugal 15 minutes.
The sucking-off supernatant liquor adds the biphosphate potassium solution, add extracting solution 3ml concussion 20 minutes, centrifugal 15 minutes, the sucking-off organic phase, surplus liquid repeats extracting once, merge organic phase, standing over night, second day sucking-off upper organic phase, nitrogen slowly dries up in 40 ℃ of-50 ℃ of water-baths,-20 ℃ of preservations are to be measured. and with the dissolving of 1ml moving phase, draw 100 μ l injection high performance liquid phase and measure during mensuration.
The making of 4 typical curves
4.1. the preparation reference liquid accurately takes by weighing the pure product of 10mg quinamine alcohol, is dissolved in the 100ml volumetric flask with moving phase, as first stock solution, draw the first stock solution 1ml, in the brown volumetric flask of 25ml, concentration is 4000ng/ml, as second stock solution with the moving phase constant volume.Draw the second stock solution 0.625ml, 1ml, 1.5ml, 2ml, 2.5ml, 3ml, 4ml, 5ml, concentration is respectively 100ng/ml, 160ng/ml, 240ng/ml, 320ng/ml, 400ng/ml, 480ng/ml, 640ng/ml, 800ng/ml.
Organize 2g 4.2. take by weighing blank, press method for making sample and handle, add each the concentration standard liquid 1ml for preparing during mensuration, HPLC measures, and makes typical curve by peak area and concentration.
5. the mensuration of the rate of recovery
5.1 the preparation of medicine accurately takes by weighing the pure product of 10mg quinamine alcohol, is dissolved in the 100ml volumetric flask with acetonitrile, as first stock solution, draws the first stock solution 1ml, in the brown volumetric flask of 25ml, concentration is 4000ng/ml, as second stock solution with the acetonitrile constant volume.Draw the second stock solution 0.625ml, 2ml, 4ml, 5ml, concentration is respectively 100ng/ml, 320ng/ml, 640ng/ml, 800ng/ml.
Organize 2g 5.2 take by weighing blank, the reference liquid of each concentration that adding 2ml prepares, homogenate 5 minutes adds the 2ml acetonitrile again and mixes, the accurately even homogenate that is equivalent to the 1g tissue, the as follows method for making sample got.Last machine calculates concentration by typical curve, again calculate recovery rate after measuring.
6. experimental animal grouping and sampling are divided into 8 groups at random with 32 of the blank chickens in first experiment, 4 every group, observe a week, chicken health.Use the capsule dose regimen at 20 o'clock in evening October 3, administration 50ppm was administered once every 12 hours, and administration is 6 times altogether.Sampling time is followed successively by 2,6, and 12,18,24,36,48,72 hours, after the administration 2 hours the last time, cut open and kill, get muscle, liver, kidney are loaded in the white valve bag, and be to be measured in-20 ℃ of refrigerators.
Sample determination carries out according to the sample preparation program, afterwards through the HPLC measurement result
Quinamine alcohol is at muscle, liver, and the elimination time in the kidney is 37.57,38.06,39.31 hours, so withdrawal time is decided to be 2 days.
Quinamine alcohol is studied the broiler chicken subacute toxicity test:
Select 222 Ai Wei mattress chick for use, be divided into for 2 phases, carry out subacute feeding experiment respectively.4 groups of the first phases, every group of 25 chickens, first group is the blank group, 2-4 organizes and adds quinamine alcohol 100mg, 150mg and 300mg in every kilogram of feed respectively; The second phase is divided into 4 groups, every group of 18 chickens, and first group is the blank group, 2-4 organizes and adds quinamine alcohol 250mg, 500mg and 1000mg in every kilogram of feed respectively.The first phase is measured the index of the urea N (BUN) that respectively organizes in the chicken serum, creatinine (Cr), gpt (ALT), glutamic-oxal(o)acetic transaminase (AST) at 20d, 30d, 40d; The second phase is measured organ coefficient and serum BUN, Cr, ALT, AST index respectively at 10d, 20d, 30d.ALT, AST, BUN, Cr, detection index show, adds quinamine alcohol 50-1000ppm in the feed and all do not have significant difference (p〉0.05) with the blank group; Histopathology detects and shows, adds quinamine alcohol 50-150ppm in the feed body heart, liver, kidney, lungs and Digestive tract weave construction are not all had obvious visible influences; Organ coefficient detect to show, add 250-1000ppm quinamine alcohol and blank group in the feed and do not have significant difference (p〉0.05), but when feeding quinamine alcohol 10d when kidney, 30d the fabricius bursa occur significant difference (p〉0.05 and (p＜0.01).
As the good new variety of medicated feed additive, small white mouse is adopted in test, and LD50 is that 9000mg/kg, broiler chicken LD50 are 4949.94mg/kg.It has tangible fungistatic effect to intestinal bacteria, Salmonellas etc.; Preventive effect to the white scour of chicken, yellow scour of piglet is higher than olaquindox 15-20%, can obviously improve weight gain of piglets and efficiency of feed utilization, reduces the generation of dysentery.
Quinamine alcohol Shu quinoxaline derivative has on the one hand the antibacterial effect of wide spectrum, especially the digestive tract diseases due to the Gram-negative bacterias such as intestinal bacteria, Salmonella is had good effect, thereby improves the speed of growth.Can influence animal body intracellular metabolite (particularly endocrine system) on the other hand and promote protein assimilation, it is synthetic to increase protein in body, improve the effect improved feed conversion rate that utilizes of energy in the feed, improve the biological value of nitrogen, make more nitrogen be stored in the effect that presents promotes growth and voluminous lean meat in the body, with olaquindox, carbadox, western a word used for translation oxygen are compared, do not have and cause a disease teratogenesis, carinogenicity effect.
The preparation method of quinamine alcohol of the present invention has following beneficial effect:
Can obtain anti-microbial activity and growth promoting function height by this preparation method, the quinamine alcohol crystal that toxicity is low.
Embodiment
Now technical solution of the present invention is described further by following embodiment.
The chemical synthesis process of quinamine alcohol is:
(1) 18.3g (0.133mol) o-Nitraniline and 0.42g (0.0013mol) Tetrabutyl amonium bromide are dissolved in the 70g toluene, 50% aqueous sodium hydroxide solution that adds 25.3g (0.266mol), stir down at 15-20 ℃, slowly splash into 127g (0.185mol) aqueous sodium hypochlorite solution (available chlorine content is 5.2%), continue down to stir 3 hours at 15-20 ℃ then, divide the phase of anhydrating, get the toluene solution of benzo furazan-1-oxide compound, under vacuum, boil off toluene, get benzo furazan-1-oxide compound of 17.4g;
(2) the benzo furazan-1-oxide compound of 16.2g and the methyl ethyl diketone of 13.5g are dissolved in the triethylamine of 30ml, allow this solution at room temperature leave standstill 18 hours, collecting precipitation can get 2-ethanoyl-3 Jia based quinoxaline-1 of 16g after the drying, 4 dioxide get pure product through recrystallizing methanol;
(3) with the 2-ethanoyl Jia based quinoxaline-1 of 5g; 4 dioxide are dissolved in the furtural of 10g, are heated to 50-80 ℃ of dissolving, are placed on and are cooled to 20-35 ℃ in the mixture of ice and water; slowly pour the 4ml diethylamine into; color gradually becomes brown, in entry, continues to stir; there is precipitation to separate out; suction filtration obtains thick product, and ethyl alcohol recrystallization obtains the pure product of quinamine alcohol.
Claims (1)
1, the preparation method of quinamine alcohol is characterized by:
(1) 18.3g o-Nitraniline and 0.42g Tetrabutyl amonium bromide are dissolved in the 70g toluene, 50% aqueous sodium hydroxide solution that adds 25.3g, stir down at 15-20 ℃, splash into the 127g aqueous sodium hypochlorite solution, continue down to stir at 15-20 ℃ then, divide the phase of anhydrating, get the toluene solution of benzo furazan-1-oxide compound, under vacuum, boil off toluene, get benzo furazan-1-oxide compound of 17.4g
(2) the benzo furazan-1-oxide compound of 16.2g and the methyl ethyl diketone of 13.5g are dissolved in the triethylamine of 30ml, allow this solution at room temperature leave standstill, collecting precipitation can get 2-ethanoyl-3 Jia based quinoxaline-1,4 dioxide after the drying,
(3) with the 2-ethanoyl-3 Jia based quinoxaline-1 of 5g; 4 dioxide are dissolved in the furtural of 10g, are heated to dissolving, are placed on to be cooled to 20-35 ℃ in the mixture of ice and water; slowly pour the 4ml diethylamine into; color gradually becomes brown, in entry, continues to stir; there is precipitation to separate out; suction filtration obtains thick product, and ethyl alcohol recrystallization obtains the pure product of quinamine alcohol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796051A (en) * | 2012-09-11 | 2012-11-28 | 湖北中牧安达药业有限公司 | Preparation method of mequindox |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172621B (en) * | 2013-03-15 | 2015-08-05 | 广东省天宝生物制药有限公司 | A kind of preparation method of quinamine alcohol of improvement |
| CN104841399B (en) * | 2015-05-06 | 2017-07-07 | 华中农业大学 | A kind of preparation method and application of the formaldehyde Isosorbide-5-Nitrae dioxy affinity substrate of quinoxaline 2 |
| CN105732525A (en) * | 2016-03-24 | 2016-07-06 | 中国农业大学烟台研究院 | Preparation method of 3-methyl-2-acetylphenylhydrazonequinoxalinyl-1,4-dioxide |
| CN108426996B (en) * | 2017-02-15 | 2020-09-15 | 江苏美正生物科技有限公司 | Rapid detection kit for 3-methyl quinoxaline-2-carboxylic acid residues and preparation method and application thereof |
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| CN1057836A (en) * | 1990-07-04 | 1992-01-15 | 能源部西安热工研究所 | The preparation method of 2-hydroxyl quinoline quinoline |
| CN1197068A (en) * | 1997-04-21 | 1998-10-28 | 中国农业科学院中兽医研究所 | Compound and synthetic process of 3-methyl-2-phenylethylene keto-quinooxaline-1.4-dioxide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057836A (en) * | 1990-07-04 | 1992-01-15 | 能源部西安热工研究所 | The preparation method of 2-hydroxyl quinoline quinoline |
| CN1197068A (en) * | 1997-04-21 | 1998-10-28 | 中国农业科学院中兽医研究所 | Compound and synthetic process of 3-methyl-2-phenylethylene keto-quinooxaline-1.4-dioxide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796051A (en) * | 2012-09-11 | 2012-11-28 | 湖北中牧安达药业有限公司 | Preparation method of mequindox |
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