CN103012091A - Method for preparing 3,4-dihydroxy benzaldehyde through copper oxide lattice oxygen oxidation - Google Patents
Method for preparing 3,4-dihydroxy benzaldehyde through copper oxide lattice oxygen oxidation Download PDFInfo
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- CN103012091A CN103012091A CN2011102833054A CN201110283305A CN103012091A CN 103012091 A CN103012091 A CN 103012091A CN 2011102833054 A CN2011102833054 A CN 2011102833054A CN 201110283305 A CN201110283305 A CN 201110283305A CN 103012091 A CN103012091 A CN 103012091A
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Abstract
The invention relates to a method for preparing 3,4-dihydroxy benzaldehyde through copper oxide lattice oxygen oxidation. According to the invention, water, powdery cuprous oxide, and a 30-32wt% sodium hydroxide solution with a weight ratio of 2:1-1.2:2-2.3 are added into an autoclave; oxygen is delivered in; a reaction is carried out for 3-4h under a pressure of 0.15-0.25MPa and a temperature of 105-120 DEG C, such that copper oxide lattice oxygen is obtained; 3,4-dihydroxy mandelic acid, a 30-32wt% sodium hydroxide solution, and the copper oxide lattice oxygen with a weight ratio of 1:1.8-2:1.4-1.5 are subjected to a reaction, wherein a reaction temperature is 95-102 DEG C, and a reaction time is 7-8h; a filtrate is acidified by using 50% sulfuric acid until a pH value is 1.5-2, such that 3,4-dihydroxy benzaldehyde is obtained; and a filter cake is cuprous oxide which can be recycled. According to the invention, the copper oxide lattice oxygen oxidant has high selectivity, and can be repeatedly used. A 3,4-dihydroxy benzaldehyde yield reaches 95wt%.
Description
Technical field:
The present invention relates to pyrocatechol and oxoethanoic acid through 3 of condensation reaction preparation, 4-dihydroxyl amygdalic acid is raw material, replaces gas phase oxygen with the cupric oxide lattice oxygen, and oxidation prepares the method for 0412.
Background technology:
0412, another name: rancinamycin IV.A kind of important organic synthesis raw material and medicine intermediate.At present, China is wider in the research of the mechanism aspect the drug application and medical aspect to this product, and it is to separate the activeconstituents that obtains by in holly plant folium ilicis chinensis and the Chinese medicines such as the salvia red sage root.Pharmacological evaluation shows that 0412 has anticoagulant and increases the effect of coronary flow, and gold-coloured staphylococci is had certain restraining effect, can alleviate the uncomfortable in chest and angina pectoris symptom of patients with coronary heart disease.Because 3,4 Dihydroxy benzaldehydes contain reactive hydrogen compound can with the condensation of Ammonia derivative, so it is extremely derivative of antiphlogistic drug Anoretic, new cephalosporin antibiotic Cephalosporin, and the critical materials of semisynthetic antibiotics Antiarone-F, also be for the synthesis of medicines such as ring-type contracting rancinamycin IV AID and antishock vasoactive drug dopamine hydrochloride, suprarenin.
At present via pyrocatechol and oxoethanoic acid through 3 of condensation reaction preparation, 4-dihydroxyl amygdalic acid is raw material, 3,4 Dihydroxy benzaldehydes that oxidation obtains all adopt air or oxygen as oxygenant, carry out oxidation and obtain under catalyst action.
The people such as Wang Junhua in 2004 have delivered the Chinese patent (CN1508112) of " production technique of 3,4-gentisaldehyde ", and patent has only been made simple report.This technique is with pyrocatechol and the oxoethanoic acid condensation reaction generates 3,4-dihydroxyl amygdalic acid and compound mantoquita carries out oxidation, and decarboxylic reaction has generated 0412.But this technique exists yield low, the deficiency that catalyzer can not reuse.Patent (application number 200810222389.9) in 2008 " air catalytic oxidation synthetic 3; method of 4-Dihydroxy benzaldehyde " is improved, adopting the polycomponent composite type metallic oxide is catalyzer, carry out oxidation with air or purity oxygen as oxygenant, the preparation 0412.As oxygenant, under the comparatively high temps 3, there is the transition oxidative phenomena in 4-dihydroxyl amygdalic acid to this technique, causes selectivity low, yield 90wt% with air and pure oxygen.
Summary of the invention:
The object of the present invention is to provide a kind of with cupric oxide lattice oxygen replaces air and pure oxygen as oxygenant, make 3,4-dihydroxyl amygdalic acid generation oxidation prepare the method for 0412.Its preparation process is as follows:
The preparation oxygenant: the preparation of cupric oxide lattice oxygen is carried out in autoclave, adds successively the sodium hydroxide solution of end water, powdery Red copper oxide and 30wt%～32wt% in the autoclave, and weight ratio is 2: 1～1.2: 2～2.3.The enclosed high pressure still passes into oxygen, under 105～120 ℃ of pressure 0.15～0.25MPa, temperature, reacts 3～4 hours, suction strainer after reaction finishes, and the oxygenant of cupric oxide lattice oxygen that obtains being rich in lattice oxygen is for subsequent use.
3, the oxidation of 4-dihydroxyl amygdalic acid: in the reactor of condenser is housed, will by pyrocatechol and oxoethanoic acid through condensation course obtain 3,4-dihydroxyl amygdalic acid (content 4.5～5wt%), join in the reactor, under stirring, add successively again the sodium hydroxide solution of 30wt%～32wt% and the oxygenant of the above-mentioned cupric oxide lattice oxygen that makes; 3,4-dihydroxyl amygdalic acid (100wt%) is 1: 1.8～2: 1.4～1.5 with the weight ratio of sodium hydroxide solution and oxygenant.95～102 ℃ of control temperature of reaction were reacted 7～8 hours, reacted complete, suction strainer, and filtrate to pH=1.5～2, gets 0412 with the 50wt% sulfuric acid acidation.Filter cake is the Red copper oxide that is reduced, and Red copper oxide recycles at the oxygenant that again is prepared into the cupric oxide lattice oxygen.
Document and patent report oxygenant adopt pure oxygen or air before, have 3, the transition oxidation of 4-dihydroxyl amygdalic acid, also can cause simultaneously ortho position amygdalic acid (I) in the condensated liquid and the oxidative phenomena of ortho para two contracting things (II), cause that the oxidation solution color is dark, tar is many, affect the deficiencies such as postorder operation.
Previous patent adopts pure oxygen or air as the oxygenant poor selectivity, yield 90wt%.The present invention compared with prior art has following significant effect:
(1) the present invention does not have to react under the condition of gas phase oxygen molecule, but adopts molecular lattice oxygen to carry out oxidation, presses redox (Redox) pattern, can avoid gas phase that the material deep oxidation is reacted.Adopt intermolecular lattice oxygen as oxygenant, increased substantially the selectivity of product aligning amygdalic acid, made two contracting things (II) of ortho position amygdalic acid (I) and ortho para oxidized hardly, product 3,4-Dihydroxy benzaldehyde content is high, and oxidation solution is coal-tar middle oil few.
(2) press the redox pattern, the copper oxide reduction after the oxidation becomes Red copper oxide, can reprocessing cycle use.
Embodiment:
Now by embodiment the present invention is described in detail as follows:
Embodiment 1
(1) takes by weighing the sodium hydroxide solution 210g of 200g water, powdery Red copper oxide 100g and 30wt%, drop in the autoclave Sealing Arrangement, under stirring, pass into oxygen, control pressure 0.18～0.20MPa, be warming up to 105～108 ℃, under this temperature, pressure, reacted 4 hours.Suction strainer after reaction finishes, the cupric oxide lattice oxygen oxygenant that obtains being rich in lattice oxygen is for subsequent use.
(2) in the reactor of condenser is housed, drop into 3 of content 4.80wt%, 4-dihydroxyl amygdalic acid 100g, stir lower, add successively again the sodium hydroxide solution 9g of 30wt% and the cupric oxide lattice oxygen oxygenant 7g that above-mentioned (1) makes, be warming up to 95 ℃, reaction is 8 hours under this temperature.React complete, the oxidation solution suction strainer, filtrate to pH=1.5～2, gets 0412, content 88.53wt%, oxidization-hydrogenation ratio 95.80wt% with the 50wt% sulfuric acid acidation.Filter cake is the Red copper oxide that is reduced, and Red copper oxide is prepared into the oxygenant of the cupric oxide lattice oxygen of lattice oxygen again by above-mentioned (1) method, recycles.
Embodiment 2
(1) takes by weighing the sodium hydroxide solution 210g of 200g water, powdery cupric oxide 100g and 30wt%, drop in the autoclave Sealing Arrangement, under stirring, pass into oxygen, control pressure 0.2～0.23MPa, be warming up to 110～110 ℃, under this temperature, pressure, reacted 4 hours.Suction strainer after reaction finishes, the oxygenant of cupric oxide lattice oxygen that obtains being rich in lattice oxygen is for subsequent use.
(2) in the reactor of condenser is housed, drop into 3 of content 4.80wt%, 4-dihydroxyl amygdalic acid 100g, stir lower, add successively again the sodium hydroxide solution 9g of 30wt% and the oxygenant 7g that above-mentioned (1) makes the cupric oxide lattice oxygen that is rich in lattice oxygen, be warming up to 100 ℃, reaction is 7.5 hours under this temperature.React complete, the oxidation solution suction strainer, filtrate to pH=1.5～2, gets 0412, content 88.64wt%, oxidization-hydrogenation ratio 96.03wt% with the 50wt% sulfuric acid acidation.Filter cake is the Red copper oxide that is reduced, and Red copper oxide is prepared into the oxygenant of the cupric oxide lattice oxygen of lattice oxygen again by above-mentioned (1) method, recycles.
Embodiment 3
(1) takes by weighing the sodium hydroxide solution 210g of 200g water, powdery cupric oxide 100g and 30wt%, drop in the autoclave Sealing Arrangement, under stirring, pass into oxygen, control pressure 0.23～0.25MPa, be warming up to 115～118 ℃, under this temperature, pressure, reacted 3.5 hours.Suction strainer after reaction finishes, the oxygenant of cupric oxide lattice oxygen that obtains being rich in lattice oxygen is for subsequent use.
(2) in the reactor of condenser is housed, drop into 3 of content 4.80wt%, 4-dihydroxyl amygdalic acid 250g, stir lower, add successively again the sodium hydroxide solution 24g of 30wt% and the oxygenant 18g that above-mentioned (1) makes the cupric oxide lattice oxygen that is rich in lattice oxygen, be warming up to 102 ℃, reaction is 7 hours under this temperature.React complete, the oxidation solution suction strainer, filtrate to pH=1.5～2, gets 0412, content 88.70wt%, oxidization-hydrogenation ratio 95.75wt% with the 50wt% sulfuric acid acidation.Filter cake is the Red copper oxide that is reduced, and Red copper oxide is prepared into the oxygenant of cupric oxide lattice oxygen again by above-mentioned (1) method, recycles.
Embodiment 4
(1) takes by weighing 200g water, the Red copper oxide 100g that reclaims by embodiment 1～3 technique and the sodium hydroxide solution 210g of 32wt%, drop in the autoclave, Sealing Arrangement, stir lower, pass into oxygen, control pressure 0.2～0.23MPa is warming up to 110～110 ℃, under this temperature, pressure, reacted 4 hours.Suction strainer after reaction finishes, the oxygenant of cupric oxide lattice oxygen that obtains being rich in lattice oxygen is for subsequent use.
(2) in the reactor of condenser is housed, drop into 3 of content 4.68wt%, 4-dihydroxyl amygdalic acid 100g, stir lower, add successively again the sodium hydroxide solution 9g of 30wt% and the oxygenant 7g that above-mentioned (1) makes the cupric oxide lattice oxygen that is rich in lattice oxygen, be warming up to 95 ℃, reaction is 8 hours under this temperature.React complete, the oxidation solution suction strainer, filtrate to pH=1.5～2, gets 0412, content 89.04wt%, oxidization-hydrogenation ratio 95.72wt% with the 50wt% sulfuric acid acidation.Filter cake is the Red copper oxide that is reduced, and Red copper oxide is prepared into the oxygenant of cupric oxide lattice oxygen again by above-mentioned (1) method, recycles.
Embodiment 5
(1) takes by weighing 200g water, the Red copper oxide 100g that reclaims by embodiment 4 techniques and the sodium hydroxide solution 210g of 30wt%, drop in the autoclave, Sealing Arrangement, stir lower, pass into oxygen, control pressure 0.2～0.23MPa is warming up to 110～110 ℃, under this temperature, pressure, reacted 4 hours.Suction strainer after reaction finishes, the oxygenant of cupric oxide lattice oxygen that obtains being rich in lattice oxygen is for subsequent use.
(2) in the reactor of condenser is housed, drop into 3 of content 4.68wt%, 4-dihydroxyl amygdalic acid 100g, stir lower, add successively again the sodium hydroxide solution 9g of 30wt% and the oxygenant 7g that above-mentioned (1) makes the cupric oxide lattice oxygen that is rich in lattice oxygen, be warming up to 102 ℃, reaction is 7 hours under this temperature.React complete, the oxidation solution suction strainer, filtrate to pH=1.5～2, gets 0412, content 88.47wt%, oxidization-hydrogenation ratio 95.02wt% with the 50wt% sulfuric acid acidation.Filter cake is the Red copper oxide that is reduced, and Red copper oxide is prepared into the oxygenant of cupric oxide lattice oxygen again by above-mentioned (1) method, recycles.
Embodiment 6
(1) takes by weighing 200g water, the Red copper oxide 100g that reclaims by embodiment 4 techniques and the sodium hydroxide solution 210g of 32wt%, drop in the autoclave, Sealing Arrangement, stir lower, pass into oxygen, control pressure 0.23～0.25MPa is warming up to 115～118 ℃, under this temperature, pressure, reacted 4 hours.Suction strainer after reaction finishes, the oxygenant of cupric oxide lattice oxygen that obtains being rich in lattice oxygen is for subsequent use.
(2) in the reactor of condenser is housed, drop into 3 of content 4.68wt%, 4-dihydroxyl amygdalic acid 250g, stir lower, add successively again the sodium hydroxide solution 23g of 32wt% and the oxygenant 17g that above-mentioned (1) makes the cupric oxide lattice oxygen that is rich in lattice oxygen, be warming up to 102 ℃, reaction is 7.5 hours under this temperature.React complete, the oxidation solution suction strainer, filtrate to pH=1.5～2, gets 0412, content 89.07wt%, oxidization-hydrogenation ratio 95.90wt% with the 50wt% sulfuric acid acidation.Filter cake is the Red copper oxide that is reduced, and Red copper oxide is prepared into the oxygenant of cupric oxide lattice oxygen again by above-mentioned (1) method, recycles.
Claims (1)
1. cupric oxide lattice oxygen oxidation prepares the method for 0412, it is characterized in that:
Concrete steps are as follows:
(1) preparation of cupric oxide lattice oxygen: add successively the sodium hydroxide solution of entry, powdery Red copper oxide and 30～32wt% in the autoclave, weight ratio is 2: 1～1.2: 2～2.3; The enclosed high pressure still passes into oxygen, under 105～120 ℃ of pressure 0.15～0.25MPa, temperature, reacts 3～4 hours, suction strainer after reaction finishes, and the oxygenant that obtains the cupric oxide lattice oxygen is for subsequent use;
(2) in the reactor of condenser is housed, 3 of the content 4.5～5wt% that will be obtained through condensation course by pyrocatechol and oxoethanoic acid, 4-dihydroxyl amygdalic acid, join in the reactor, under stirring, add successively again the sodium hydroxide solution of 30～32wt% and the cupric oxide lattice oxygen oxygenant that step (1) makes; The weight ratio of 3,4-dihydroxyl amygdalic acid and sodium hydroxide solution and oxygenant is 1: 1.8～2: 1.4～1.5; 95～102 ℃ of control temperature of reaction were reacted 7～8 hours, reacted complete, suction strainer, and filtrate to pH=1.5～2, gets 0412 with the 50wt% sulfuric acid acidation; Filter cake is the Red copper oxide that is reduced, and Red copper oxide is prepared into the oxygenant of cupric oxide lattice oxygen again with step (1), recycles.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5466639A (en) * | 1977-11-08 | 1979-05-29 | Ube Ind Ltd | Preparation of monoformylated phenol |
| US4165341A (en) * | 1977-02-04 | 1979-08-21 | Ube Industries, Ltd. | Process for preparing protocatechualdehyde and its derivatives |
| JPS5522614A (en) * | 1978-08-04 | 1980-02-18 | Ube Ind Ltd | Preparation of formylated phenol compound |
| CN1508112A (en) * | 2002-12-20 | 2004-06-30 | 王俊华 | Process for producing 3,4-dihydroxy benzaldehyde |
| CN101676253A (en) * | 2008-09-18 | 2010-03-24 | 中国石油天然气股份有限公司 | Method for synthesizing 3,4-dihydroxy benzaldehyde by using air catalytic oxidation |
-
2011
- 2011-09-22 CN CN2011102833054A patent/CN103012091A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4165341A (en) * | 1977-02-04 | 1979-08-21 | Ube Industries, Ltd. | Process for preparing protocatechualdehyde and its derivatives |
| JPS5466639A (en) * | 1977-11-08 | 1979-05-29 | Ube Ind Ltd | Preparation of monoformylated phenol |
| JPS5522614A (en) * | 1978-08-04 | 1980-02-18 | Ube Ind Ltd | Preparation of formylated phenol compound |
| CN1508112A (en) * | 2002-12-20 | 2004-06-30 | 王俊华 | Process for producing 3,4-dihydroxy benzaldehyde |
| CN101676253A (en) * | 2008-09-18 | 2010-03-24 | 中国石油天然气股份有限公司 | Method for synthesizing 3,4-dihydroxy benzaldehyde by using air catalytic oxidation |
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Application publication date: 20130403 |