CN1024657C - Process for preparing salicylal from salicylcohol by catalytic oxidation of non-noble metal complex - Google Patents
Process for preparing salicylal from salicylcohol by catalytic oxidation of non-noble metal complex Download PDFInfo
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- CN1024657C CN1024657C CN 89105025 CN89105025A CN1024657C CN 1024657 C CN1024657 C CN 1024657C CN 89105025 CN89105025 CN 89105025 CN 89105025 A CN89105025 A CN 89105025A CN 1024657 C CN1024657 C CN 1024657C
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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Abstract
The present invention relates to a method for preparing salicyl aldehyde from salicyl alcohol, which is characterized in that the method uses a non-noble metal complex compound as a catalyst and air or oxygen gas is led into a reaction system to carry out reaction of catalytic oxidation at the temperature between 10 and 110 DEGC. the reaction condition is easy to control, the selectivity is good, and the conversion rate is high; additionally, by using the present invention, the yield of salicyl aldehyde prepared by using pure salicyl alcohol as raw material can reach 97%, and the yield of salicyl aldehyde prepared by using salicyl alcohol products which are prepared after the condensation of phenol and formaldehyde can reach higher than 80%.
Description
The present invention is a kind of preparation method of compound salicylic aldehyde, exactly, is to carry out catalytic oxidation with the preparation salicylic aldehyde by saligenol with the base metal complex compound catalyst.
Salicylic aldehyde is the important chemical product, is mainly used in synthesizing coumarin, also is used for synthetic pesticide, dyestuff intermediate and fortifying of petroleum products.The production method of salicylic aldehyde much mainly contains four kinds:
(1) with phenol and chloroform is the Reimer-Tiemann method of raw material;
(2) ortho-cresol ester chlorination process;
(3) Whitfield's ointment electrolytic reduction;
(4) phenol formaldehyde (PF) condensation, oxidation style.
In these methods, because salicylic aldehyde productive rate low (method (1)), chloridely in the product be difficult for removing (method (2)), production expends a large amount of electricity shortcomings such as (method (3)), limit its application, (4) kind method, because its raw material phenol and formaldehyde are inexpensive, reaction process is not introduced objectionable impurities, pollution is light, efficient is higher.Thereby the industrial application future is bigger, and the document of research and report is also more.As U.S. Pat 3673257; US4190605, US4306083; US4324922; Deutsches Reichs-Patent DE2620254; DE2612844; DE2736523; DE2923805; French Patent FR2498180 etc.With technology of the present invention comparatively approaching be U.S. Pat 4481374.The technology that is adopted is many to be Primary Catalysts with precious metal palladium or platinum, though these catalyzer are active higher, selectivity is also better, but catalyst recovery difficulty in the reaction process, so production cost height, though be catalyzer with the base metal metal-salt among the US4481374, the highly basic that reaction needed is a large amount of and in big water gaging, add water-soluble solvent and make the product separation difficulty.
Purpose of the present invention provides a kind of method of catalyzed oxidation legal system salicylic aldehyde.This method uses the base metal complex compound to make catalyzer, can be salicylic aldehyde with the salicylic aldehyde catalyzed oxidation under mild reaction conditions, the reaction conversion ratio height, and selectivity is good, and this method is used for the salicylic aldehyde that phenol one formaldehyde condensation, oxidation style can obtain high yield.
The salicylic aldehyde catalytic oxidation carries out (M is: Na, K) by following formula having in the presence of the alkali (MOH):
（1）
Intermediate product phenol metal-salt is dissolved in water, through acidifying, steam distillation, make salicylic aldehyde.
Phenol one formaldehyde condensation legal system salicylic aldehyde of the present invention more as shown in Figure 1 through the schematic flow sheet of oxidation system salicylic aldehyde, among Fig. 1: 1, oxidation; 2, distillation; 3, acidifying; 4, steam distillation; 5, refining.Specifically raw material phenol and formaldehyde through catalyzing and condensing react saligenol, utilize metal complex catalyst of the present invention, make under an amount of alkali (NaOH or KOH) and the solvent existence condition saligenol by oxygen institute oxidation in the air, reaction after product through distill solid phenates and reclaim solvent, the intermediate product phenates carries out acidifying after water dissolution, utilize water vapor distill thick salicylic aldehyde, after refining the finished product product.
The base metal complex catalyst that the present invention uses is schiff base or beta-diketon class.It consists of:
1, schiff base:
Wherein: E=H, CH
3,
R＝（-CH
2-）
n，
n＝2，3，4
M＝Co，Mn，Cu，VO。
2, beta-diketon class
Wherein: M=Co, Mn, Cu, V;
Catalyst consumption does not have certain restriction in the reaction process, but too much use catalyzer is to promoting the catalyzed reaction DeGrain, and increases the salicylic aldehyde production cost, and preferable usage quantity is every mol saligenol 0.1～0.005 mol catalyzer.
Add a certain amount of organic solvent in the reaction, for example: pyrrolidone, HMPA, dimethyl formamide, pyridine, methyl alcohol, ethanol, propyl alcohol, methyl-sulphoxide.The amount of using solvent in the reaction does not make significant difference to the yield of product salicylic aldehyde, but concentration of reactants is low excessively, and solvent load is excessive, and the separation of product is brought difficulty.Excessive concentration, the reaction running becomes difficult, and the reaction times also will increase.Therefore adding solvent in reaction system, to make the concentration of saligenol be 10～40%(weight), the concentration of preferable saligenol is 15～35%.
Add an amount of highly basic in the reaction, for example NaOH, KOH etc. are the most convenient with NaOH, and the alkali consumption is that every mol saligenol uses 0.5～4 mol alkali to be advisable.Reaction (1) was carried out fully inadequately when the consumption of every mol saligenol alkali was less than 0.5 mol, influenced the yield of product, and the consumption of alkali can not improve the yield of salicylic aldehyde during more than 4 mol.Acidization is become be difficult to carry out.Preferable alkali consumption is that every gram saligenol adds 0.8～2 mol alkali.
Oxidizing reaction should be controlled at 0～110 ℃ carries out, and improves the accelerated reaction of temperature of reaction energy, but temperature of reaction does not make significant difference 10～80 ℃ of preferable temperature of reaction to improving productive rate.
Salicylic aldehyde preparation process of the present invention is specific as follows:
With phenol and formaldehyde condensation reaction product or directly react with salicylic aldehyde, the adding solvent makes the concentration of saligenol be controlled at 10～40%(and weighs), every mol of pressing saligenol adds 0.5～4 mol highly basic, preferable alkali number is that 0.8～2 mol is in reactor, under agitation add catalyzer, catalyst consumption is every mol saligenol with 0.1～0.005 mol catalyzer.0～110 ℃ of control reaction temperature, preferable temperature of reaction are 10～80 ℃.React under the air or oxygen atmosphere, air pressure does not have obvious influence to the yield of reaction product, but air pressure increases oxidation rate acceleration, reaction times shortening.Reaction process air-pressure controlling 1～6Kg/Cm
2Be advisable.Solvent is distilled, reclaimed to reaction after finishing.Mineral acids such as gained phenates solid is dissolved in water, the available sulfuric acid of the used acid of acidifying, hydrochloric acid, nitric acid, acidifying after product through steam distillation with salicylic aldehyde and do not have reaction of phenol to steam, the suitably refining again finished product salicylic aldehyde that obtains.With phenol and formaldehyde is that the content of catalytic material condensation gained saligenol was not less than 30% o'clock, and the yield of salicylic aldehyde is greater than 70%.With pure saligenol is raw material, and the yield of salicylic aldehyde can reach 97%.
Example 1, schiff base catalyzer
The contract preparation of triethylenediamine cobalt Salen-Co of double salicylaldehyde
(1) the 50ml ethanolic soln of quadrol 0.02mol is splashed into to the 50ml ethanolic soln of 0.04mol salicylic aldehyde obtains the glassy yellow soup compound, heating for dissolving.
(2) the 20ml aqueous solution with the 0.02mol Cobaltous diacetate splashes into to (1) the middle reddish-brown precipitation that generates, and cooling, filtration, washing, ethanol are washed, drying obtains brick-red pressed powder.
Ultimate analysis: C56.85%; H4.1%; Co10.92%, its molecular formula is:
The contract preparation of quadrol Salen-Mn of example 2, double salicylaldehyde
(1) with example 1, (1)
(2) change the Cobaltous diacetate operation with the 0.02mol manganese acetate and obtain the khaki color pressed powder with example 1, (2).
Ultimate analysis: C57.75%H4.25%Mn18.72%, its molecular formula is:
The preparation that quadrol closes copper Salen-Cu of contracting of example 3, double salicylaldehyde
(1) presses example 1, (1) operation
(2) by example 1, (2) Cobaltous diacetate is changed as neutralized verdigris and obtain greyish-green powdered solid.
Ultimate analysis: C=58.43%H=4.27%
Cu=19.33%, its molecular formula is:
The preparation that quadrol closes vanadium Salen-VO of contracting of example 4, double salicylaldehyde
(1) presses the operation of example 1, (1)
(2) by example 1, (2) Cobaltous diacetate is changed as vanadylic sulfate and obtain posting green powder.
Ultimate analysis: C55.5%H3.96%; V16.8%, its molecular formula is:
Example 5, beta-diketon class catalyzer double salicylaldehyde close cobalt Co(Salde) 2 preparation
Neutralize ginger-colored sedimentation and filtration, washing, vacuum-drying of the 50ml ethanolic soln that the 60ml aqueous solution of 0.035ml Cobaltous diacetate is splashed into the 0.0706mol salicylic aldehyde under heating obtains ginger-colored powder.
Ultimate analysis: C55.81%; H3.32%; Co19.60%, its molecular formula is:
The preparation that example 6, two (acetylacetone based) are closed cobalt
With 2,4-diacetylmethane (40g; 0.4mol) under agitation join 16g(0.4mol lentamente) NaOH is in the 150ml aqueous solution, temperature is remained below 40 ℃, generate white solid, heating makes its dissolving, obtain yellow solution, yellow solution was splashed into 47.6g(0.2mol in 10 minutes) cobalt chloride (II) is in the aqueous solution of 250ml, obtain orange precipitation, filtration, washing, filter cake is dissolved in the hot mixt of 390ml195% ethanol and 260ml chloroform, this red solution is chilled to room temperature to be placed in the ice freezing then, orange crystallization filtration is washed with 95% ethanol, air-dry.
Ultimate analysis: C40.35; H6.02; Co20.11, its molecular formula is:
The preparation of example 10, salicylic aldehyde
Under air atmosphere, saligenol (is formed by phenol and formaldehyde condensation, contain saligenol 38%), NaOH and methanol solvate join in the reactor, under agitation add western Buddhist alkali Salen-Co catalyzer, when containing pure saligenol 0.1mol during reaction in each raw material, use methyl alcohol 70ml, add solid NaOH4g, 1 controlling catalyst 0.005mol of example.60 ℃ of temperature of reaction are reflected under the normal pressure and carry out.
Reaction is reclaimed solvent methanol after distillation obtains the solid sodium phenolate.Add 150ml water dissolution solid sodium phenolate, be acidified to PH=3 with 0.5N sulfuric acid, carry out steam distillation, divide water-yielding stratum to obtain salicylic aldehyde, the yield of its salicylic aldehyde is 82%.
In above-mentioned reaction process and the condition, be raw material as the saligenol with 99.0%, then the yield of salicylic aldehyde is 97%.
Example 11, alkali consumption are to the influence of oxidizing reaction
Reaction process and condition are as described in the example 10, and the yield of salicylic aldehyde is shown in the table 1 during the quantitative change of used NaOH.
The influence of table 1, alkali consumption
Experiment NaOH/ saligenol (mole ratio) salicylic aldehyde yield %
1 0.5 45
2 0.8 90
3 1 91
4 1.5 92
5 2 92
6 3 92
7 4 91
When the consumption of alkali more after a little while, the yield of salicylic aldehyde is lower, but excessive alkali is little to the yield influence that increases salicylic aldehyde.The consumption of alkali and the mole ratio of saligenol are that the yield of 4: 1 o'clock salicylic aldehydes reaches more than 90%, and preferable mole ratio is that every mol saligenol alkali is 0.8～2 mol.
The influence of example 12, quantity of solvent
Reaction process and condition such as example 10, the consumption of methanol solvate changes as shown in table 2 to the influence of salicylic aldehyde yield.
The yield of table 3, quantity of solvent and salicylic aldehyde
Reactant concn mol/L salicylic aldehyde rate % in the experiment methyl alcohol ml solution
1 1000 0.1 93
2 500 0.2 92
3 200 0.5 92
4 100 1.0 92
5 70 1.4 91
6 50 2 91
7 10 10 65
The result of example 12 shows that solvent load does not make significant difference to the salicylic aldehyde yield, considers separating of solvent and reaction product, the solvent load in the reaction for, preferable when making reaction soln concentration be 0.5～2mol/L, be 10～40% by weight percentage.
Claims (3)
1, a kind of oxidation saligenol prepares the method for salicylic aldehyde, it is characterized in that:
(1) with the base metal complex compound, western Buddhist alkali or beta-diketon class are as catalyzer, wherein:
A, schiff base complex compound are made up of following formula (1):
In the formula: E=H, CH
3-,
n=2，3，4
M=Co，Mn，Cu，VO；
B, beta-diketon class complex compound are made up of following formula (2);
In the formula: M=Co, Mn, Cu, V;
(2) add certain amount of organic solvent, the concentration that makes saligenol in the reaction system is 10～40% (weight):
(3) add quantitative highly basic, NaOH or KOH, its amount is used 0.5～4 mol alkali for every mol saligenol;
2, in accordance with the method for claim 1, the amount that it is characterized in that catalyst system therefor is by (mole ratio):
Catalyzer: saligenol=0.1～0.005.
3, in accordance with the method for claim 1, it is characterized in that the organic solvent that adds can be: pyrrolidone, HMPA, dimethyl formamide, pyridine, methyl alcohol, ethanol, propyl alcohol, methyl-sulphoxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105025 CN1024657C (en) | 1989-02-24 | 1989-02-24 | Process for preparing salicylal from salicylcohol by catalytic oxidation of non-noble metal complex |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105025 CN1024657C (en) | 1989-02-24 | 1989-02-24 | Process for preparing salicylal from salicylcohol by catalytic oxidation of non-noble metal complex |
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| Publication Number | Publication Date |
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| CN1045095A CN1045095A (en) | 1990-09-05 |
| CN1024657C true CN1024657C (en) | 1994-05-25 |
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