The method of obtaining substituted 4-hydroxybenzaldehyde

 

(57) Abstract:

Describes how to obtain the substituted 4-hydroxybenzaldehyde General formula V in which Z1represents an alkoxy radical, a linear or branched, having from 1 to 12 carbon atoms, predominantly from 1 to 4 carbon atoms, such as methoxy radicals, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, Z2and Z3identical or different, represent a hydrogen atom or one of the following groups: alkyl radical, linear or branched, having from 1 to 12 carbon atoms, predominantly from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, alkenyl radical, linear or branched, having from 2 to 12 carbon atoms, mostly from 2 to 4 carbon atoms, such as vinyl, allyl; alkoxy radical, a linear or branched, having from 1 to 12 carbon atoms, predominantly from 1 to 4 carbon atoms, such as methoxy radicals, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenyl radical, a halogen atom, preferably fluorine atom, chlorine or bromine. The method differs in that the substituted phenol of the is up to the carboxylation in position 6 with the connection, having the formula II, in which Z1, Z2, Z3have the above values, M is a cation of a metal of group Ia, or a Quaternary ammonium cation, then carry out a stage of hydroxymethylpropane in position 4 with obtaining compounds having the formula III in which Z1, Z2, Z3M have the above meanings, with subsequent oxidation hydroxymethylene group to the formyl group, to obtain compounds of formula IV in which Z1, Z2, Z3M have the above meanings, and at the last stage decarboxylase compound of formula IV to obtain the desired 4-hydroxybenzaldehyde formula V. the Technical result - the simplification of the process. 4 C. and 21 C.p. f-crystals, 1 PL.

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The present invention relates to a method for producing 4-hydroxybenzaldehyde, which has at least one Deputy under orthopaedie to the OH group.

The invention concerns, in particular, for the preparation of 3-methoxy-4-hydroxybenzaldehyde and 3 ethoxy-4-hydroxybenzaldehyde, called respectively "vanillin and ethylvanillin".

Vanilla comes primarily from natural raw materials, such as lignin, but some IRK-OTHMER-Encyclopedia of Chemical Technology 23, S. 1710 - 3 - publication], and many of them are based on obtaining vanillin from guaiacol or 2-methoxyphenol.

So you can refer to obtaining vanillin by the interaction of guaiacol with Glyoxylic acid oxidation in air condensate and subsequent allocation of vanilla from the reaction medium by acidification. The disadvantage of this method lies in the use of Glyoxylic acid, which is an expensive reagent.

Another way of obtaining vanillin based on the reaction of the Reimer-Tismana, and consists in the interaction of guaiacol and chloroform in the presence of potassium hydroxide. Education resin is a disadvantage of this method.

Synthesis of vanillin according to the reaction of Gatterman is in the processing of hydrocyanic acid guaiacol in the presence of hydrochloric acid. In addition, this method is used reagent, requiring careful handling, it has another disadvantage that is not selective, as with vanilla get isovanillin and orthovision.

The greatest difficulty in the synthesis of vanillin is selective fixation of the formyl group on the guaiacol in paraprotein to the hydroxyl group.

Another problem is.

The present invention provides such a method which eliminates the above disadvantages, satisfying the requirements specified above.

The object of the present invention is a method of obtaining a 4-hydroxybenzaldehyde, substituted, at least in position 3 alkoxy group, consists in the fact that phenolic compounds substituted at least in position 2 alkoxy group, and positions 4 and 6 of which are free, at the first stage is subjected to carboxylation position 6, then subjected to the next step hydroxymethylpropane position 4, then oxidize hydroxymethylene group to a formyl group and, finally, subjected to phase decarboxylation.

The method according to the invention based on receiving 2-hydroxybenzoic hydroxymethylpropane in position 5 acids, substituted at least at position 3 alkoxy group, which serve as an intermediate product in the synthesis of 4-hydroxybenzaldehyde, substituted at least at position 3 alkoxy group.

Another object of the invention is a method for the oxidation of 2-hydroxybenzoic hydroxymethylpropane in position 5 acids, substituted, at least in position 3 alkoxy-Grue well suited to produce vanillin. In fact, it allows selective formirovanie guaiacol in paraprotein, exercising consistently the carboxylation of guaiacol in position 6, hydroxymethylpropane with subsequent oxidation to the formyl group at position 4, and, finally, removal of the carboxyl group in position 6.

This method is not only selective, but also meets with the industrial point of view because it uses inexpensive reagents.

Although the method according to the invention gives excellent results with guaiacol and guatalon, it is also feasible with other substituted phenolic compounds.

Under "substituted phenolic compound" is understood any aromatic compound in which the aromatic nucleus is a carrier of a hydroxyl group, CNS group in position 2 and other possible substitutes, and positions 4 and 6 of which are free.

The following mean by the term "aromatic" classical notion of aromatics, which is defined in the literature, in particular, Jerry March, Advanced Organic Chemistry, 4th ed, John Wiley and Sons, 1992, S. 40 and following.

Of substituted phenolic compounds according to izaberete the defaults CNS radical, linear or branched, having from 1 to 12 carbon atoms, predominantly from 1 to 4 carbon atoms, such as methoxy radicals, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy,

- Z2and Z3identical or different, represent a hydrogen atom or one of the following groups:

alkyl radical, linear or branched, having from 1 to 12 carbon atoms, predominantly from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,

alkanniny radical, linear or branched, having from 2 to 12 carbon atoms, mostly from 2 to 4 carbon atoms, such as vinyl, allyl,

CNS radical, linear or branched, having from 1 to 12 carbon atoms, predominantly from 1 to 4 carbon atoms, such as methoxy radicals, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy,

phenyl radical,

halogen atom, preferably fluorine atom, chlorine or bromine.

According to the invention may be present on the aromatic ring substituents of different types, because they do not affect the reaction according to the method of the invention.

CNS radical, linear or branched, having from 1 to 6 carbon atoms, predominantly 1-4 carbon atoms; Z2and Z3means a hydrogen atom.

As preferred examples of substrates used in the method include, among others, guaiacol and svetol.

According to the proposed method are used as initial products of substituted phenolic compound, which is predominantly a compound corresponding to the formula I.

At the end of the description given reaction scheme of the method according to the invention, in order to better understand the invention, but it does not restrict the scope of the invention.

Further description will refer to these formulas.

According to the invention in the first stage, the carboxylation of substituted phenolic compounds of formula I by the interaction of the mentioned phenolic compounds in the form of a salt with carbon dioxide.

Phenol substituted compounds interact in the method according to the invention in the form of a salt. We are talking mainly about the salts with metals of group Ia of the Periodic system of chemical elements.

To determine the groups of metals and other elements in this description reference is made to Periodi of view of practical and economic use salts of sodium and potassium.

You can use the substituted phenolic compound in the form of salts obtained before the use, but you can also get salt in situ by the interaction of substituted phenolic compounds with a base.

Use in the method according to the invention the base, which may be mineral or organic.

Choose mainly a strong base, i.e., the base having an indicator pKb greater than 12: pKb value is defined as cologarithm dissociation constants measured base in water at 25oC.

Mostly use mineral bases such as alkali metal salts, preferably alkali metal hydroxide, which may be sodium hydroxide or potassium hydroxide; a carbonate of an alkali metal, mainly potassium.

You can also use the Quaternary ammonium hydroxide.

As examples of the Quaternary ammonium hydroxide is used mainly hydroxide tetralkylammonium or trialkylborane, alkalemia radicals which are identical or different, represent alkyl chain, linear or branched, having from 1 to 12 carbon atoms, predominantly from 1 to 6 carbon atoms.

According to the invention can also be used hydroxide trialkylborane, and in particular, hydroxide trimethylantimony.

Economic considerations of all bases is chosen mainly sodium hydroxide or potassium carbonate.

The concentration of the original solution the main character is not critical. The solution used in the alkali metal hydroxide has a concentration equal to typically 10-50 wt.%.

The number of base introduced into the reaction medium depends on the amount necessary to result in salt hydroxyl functions of substituted phenolic compounds.

If a named connection has other soleobrazutaya functions in addition to hydroxyl, then enter this number base, which is necessary for the transformation in Sol all salt-forming functions.

Typically, the quantity of base, expressed in relation to the substituted phenolic compound is from 90 to 120% of the stoichiometric amount.

Get substituted phenolic compound in salt form by interaction with the base at a temperature of, preferably equal 25-100oC.

Before you enter dioxide from the Institute of economy and management, or under a reduced pressure of 1 mm RT. Art. to atmospheric pressure, or by drying. When the environment is no more water is injected carbon dioxide.

Another variant of the method consists in using an anhydrous carbonate of an alkali metal, mainly anhydrous potassium carbonate, which eliminates the step of removing water (for example from 5 to 100 mol.% substituted phenolic compounds).

The amount of carbon dioxide, expressed in molar ratio between carbon dioxide and substituted phenolic compound, varies from 1 to 100 and preferably from 1 to 2.

The method according to the invention is carried out mainly at a temperature of 150-250oC, preferentially at 160-200oC.

Carry out the method according to the invention at atmospheric pressure, passing the carbon dioxide in the form of bubbles through the reaction medium supported under stirring.

You can also perform the reaction under pressure of carbon dioxide, which varies between atmospheric pressure and about 100 bars. Prefer a pressure of from 1 to 20.

The preferred method is the practical implementation of the invention consists in the fact that IP is then injected carbon dioxide. We are talking about the reaction type, the solid/gas.

At the end of the reaction produce of substituted phenolic compounds, in which the carboxylate group is in position 6, and dissolve it in water to a concentration of from 5 to 50 wt.%.

Bring the solution to a pH of 6-10, mainly close to 7 by adding acid.

You can use any acid, but because of economic reasons I prefer to use the classic mineral acids, mainly hydrochloric acid or sulfuric acid. The concentration of acid is not critical. It corresponds mainly to the concentration produced in the sale, for example, 37% wt. for hydrochloric acid and 92 or 96% sulfuric acid.

Receive, therefore, a two-phase medium consisting of an organic phase containing unreacted substituted phenolic compound, and the aqueous phase containing the expected product, namely salt of 2-hydroxybenzoic acid, at least substituted in position 3 alkoxy group, which is represented by formula I in which 1, Z2and Z3have the meanings given above and M represents a hydrogen atom and/or a cation of a metal of group Ia.

Further this is to obtain the aqueous phase.

It should be noted that the use as a source of salt hydroxybenzoic acid of the formula II obtained before the actual use, is included in the scope of the invention.

At the next stage, the reaction hydroxymethylpropane in position a pair of the OH group by reaction of the salt of the acid obtained above, with formaldehyde, if necessary in the presence of a base.

You can use formaldehyde or any connection, forming formaldehyde, such as, for example, trioxane or paraformaldehyde used in the form of linear polyformaldehyde with any degree of polymerization, which is mainly the number of links (CH2O) from 8 to 100.

Use the named reagent usually in the form of an aqueous solution having a concentration of less than 50 wt.%, mainly from 20-50 wt.%.

The quantity of formaldehyde, expressed in moles of formaldehyde per mole of salt hydroxybenzoic acid may vary over a wide range.

Mainly the molar ratio of formaldehyde/salt hydroxybenzoic acid is 0.5 to 3.0.

It is possible to conduct the reaction in the presence of a base. The grounds listed above, are very well suited for this Ania and the number of moles of salt hydroxybenzoic acid, can vary from 0 to 2 and preferably between 0 and 1.1.

The base can be used both in solid form and in the form of an aqueous solution.

The reaction temperature range is from 50oC to 100oC, and preferably from 60oC to 80oC.

The method is carried out mainly under the autogenous pressure of the reactants in order to avoid possible loss of paraformaldehyde, which can be gaseous at the temperatures used.

Prefer to conduct the reaction in an inert atmosphere such as nitrogen or noble gases such as argon.

The duration of reaction can be very different. It usually ranges from 30 minutes to 24 hours, mainly from 4 hours to 8 hours.

From a practical point of view, the reaction is easy to implement, if the installation is to apply salt hydroxybenzoic acid and formaldehyde, if needed base, then with stirring to bring the reaction mixture to the desired temperature for the time required to complete the reaction.

The order of introduction of the reagents is not critical and may vary.

At the end of the reaction get 2-hydroxybenzoic reacts mainly to the formula III, in which Z1, Z2and Z3have the meanings given above and M represents a hydrogen atom and/or a cation of a metal of group Ia.

According to a preferred variant of the method according to the invention do not emit the received connection, and put it directly oxidation.

The preferred method of oxidation according to the invention, constituting a second object of the present invention, consists in the oxidation of 2-hydroxybenzoic hydroxymatairesinol in position 5 acid, substituted, at least in position 3 alkoxy group, in the liquid phase with molecular oxygen or gas containing. Working in an aqueous medium containing an alkaline agent, in the presence of a catalyst based on platinum or palladium, if necessary in the presence of socializaton on the basis of the derived bismuth.

As for the noble metals used for the catalysis reaction, in this case, platinum and palladium, they can have different forms, such as platinum black, palladium black, platinum oxide, palladium oxide or noble metal deposited on different media, such as carbon black, calcium carbonate, aluminum oxide and activated silica or equivalen the>

The amount used of the catalyst based on the weight of platinum or palladium with respect to the weight 2-hydroxybenzenes hydroxymatairesinol acid can vary from 0.01 to 4% and preferably from 0.04 to 2%.

You can use socialization, in particular, using, as a rule, mineral-derived or derived organic bismuth, in which the bismuth atom has an oxidation state greater than zero, for example, 2, 3, 4 or 5. The remainder connected with bismuth, is not critical since, when he meets this condition. Acetalization may be soluble or insoluble in the reaction medium.

To illustrate socializaton, which can be used in the method according to the invention, are: oxides of bismuth; bismuth hydroxide; salts of mineral hydrogen acids, such as chloride, bromide, iodide, sulfide, selenide, telluride bismuth; salts of oxygen-containing mineral acid, such as sulfite, sulfate, nitrite, nitrate, postit, phosphate, pyrophosphate, carbonate, perchlorate, antimonate, arsenate, Selenite, selenate bismuth; salt derivatives of oxygen-containing acids with transition metals, such as Vanadate, niobate, tantalate, chromate, molybdate, the ox is political or aromatic acids, for example acetate, propionate, benzoate, salicylate, oxalate, tartrate, lactate, citrate of bismuth; Fenty, such as gallate and pyrogallol bismuth. These salts and fenati can also be salts vesatile.

As other mineral or organic compounds can be used binary compositions of bismuth with other elements such as phosphorus and arsenic; heteroalicyclic containing bismuth, as well as their salts, are also suitable aliphatic and aromatic bismuthine.

As specific examples are:

oxide: BiO; Bi2O3; Bi2O4; Bi2O5,

- hydroxide: Bi(OH)3,

- mineral salts hydrogen acids: chloride of bismuth BiCl3, bromide, bismuth BiBr3, iodide of bismuth BiI3the sulphide of bismuth Bi2S3the selenide bismuth Bi2Se3the telluride bismuth Bi2Te3,

- mineral salts of oxygen-containing acids: basic bismuth sulfite Bi2(SO3)3Bi2O35H2O, the neutral sulfate bismuth Bi2(SO4)3sulphate vesatile (BiO)HSO4, nitrite vesatile (BiO)NO20.5 H2O, neutral bismuth nitrate Bi(NO3)35H2)O, double nitrate of bismuth and magnesium 2Bi(NO33H2O; neutral bismuth phosphate BiPO4; pyrophosphate bismuth Bi4(P2O7)3; carbonate vesatile (BiO)2CO30.5 H2O; neutral bismuth perchlorate Bi(ClO4)35H2O; perchlorate vesatile (BiO)ClO4; antimonate bismuth BiSbO4; neutral bismuth arsenate Bi(AsO4)3; arsenate vesatile (BiO)AsO45H2O; Selenite bismuth Bi2(SeO3)3.

salts derived oxygen-containing acids of the transition metals: bismuth Vanadate BiVO4; niobate bismuth BiNbO; chantalat bismuth BiTaO4; neutral chromate of bismuth Bi2(CrO4); bichromate vesatile ((BiO)2)2Cr2O7acid chromate vesatile H(BiO)CrO4; double chromate vesatile and potassium (K) (BiO)CrO10; bismuth molybdate Bi2(MoO4)3; bismuth tungstate Bi2(WO4)3; dual-bismuth molybdate and sodium NaBi(MoO4)2; main permanganate bismuth Bi2O2(OH)MnO4;

salts of aliphatic and aromatic organic acids: acetate bismuth Bi(C2H3O2)3; propionate vesatile (BiO)C3H5O2; basic bismuth benzoate C6H5CO2Bi(OH)2; salimata Bi2(C4H4O6)36H2O; bismuth lactate (C6H9O5)OBi7H2O; citrate of bismuth C6H5O7Bi;

- fenati: basic gallate of bismuth C7H7O7Bi, the main pyrogallic bismuth C6H3(OH)2(OBi)(OH).

As other mineral and organic compounds: bismuth phosphide BiP, gallium, bismuth Bi3As4visatec sodium NaBiO3bismuth-thiocyanate acid (H2[Bi(BNS)5] , H3[Bi(CNS)6] and their salts of sodium and potassium; trimethylamin Bi(CH3)3triphenylbismuth Bi(C6H5)3.

Derivatives of bismuth, which are mainly used for carrying out the method according to the invention, are: bismuth oxide, bismuth hydroxide, bismuth salt or vesatile mineral hydrogen acids, salts of bismuth or vesatile oxygen-containing mineral acids, salts of bismuth or vesatile aliphatic or aromatic organic acids, and fenati bismuth or vesatile.

Group socialization, which are particularly suitable for carrying out the invention consists of: oxides of bismuth Bi2O3and Bi2O4, bismuth hydroxide Bi(OH)3neutral Sul the BiI3neutral bismuth nitrate Bi(NO3)35H2O; nitrate vesatile BiO(NO3); carbonate vesatile (BiO)2CO30.5 H2O; acetate bismuth Bi(C2H3O2)3; musk vesatile C6H4CO2(BiO)(OH).

The number of acetalization, expressed through the number of metallic bismuth contained in socializaton, relative to the weight is taken of the noble metal can vary over a wide range. For example, this number can be as small of 0.1%, and can reach a weight of used noble metal and even exceed it without negative consequences.

In particular, this number is chosen so that it was made on Wednesday oxidation from 10 to 900 ppm weight of metallic bismuth in relation to 2-hydroxybenzoic hydroxymatairesinol acid. This purpose can be used number of socializaton about 900-1500 ppm, however, without significant additional benefits.

According to the method according to the invention, the oxidation is carried out in an aqueous medium containing in solution an alkaline agent. To do this, as the alkaline agent used is usually sodium hydroxide or potassium. For the 2-hydroxybenzoic hydroxymatairesinol acid.

The concentration of 2-hydroxybenzoic hydroxymatairesinol acid in an aqueous solution of an alkaline agent should preferably be such as to avoid the formation of sludge and to maintain a homogeneous solution.

The weight concentration of 2-hydroxybenzoic hydroxymatairesinol acid in the aquatic environment is usually equal to 1-60%, mainly 2-30%.

In practice, the implementation of the method according to the invention consists in the fact that it was making contact with molecular oxygen or gas containing, for example with air, water solution, oxidized 2-hydroxybenzoic hydroxymatairesinol acid alkaline agent, a catalyst based on platinum or palladium and, if necessary, of socializaton on the basis of the derived bismuth according to the above ratios.

Work at atmospheric pressure, but if necessary you can also work at a pressure equal to 1-20 bar.

The mixture is then stirred at the desired temperature until it is consumed, the amount of oxygen, which corresponds to the quantity necessary for the conversion of the alcohol function into a function of the aldehyde. Thus, the course of the reaction is monitored by measuring the absorbed if the of FL.

Usually the reaction is carried out in the temperature range 50-100oC, mostly 60-80oC.

At the end of the reaction, which lasts mainly from 30 minutes to 2 hours, get 2-hydroxybenzoic formulirovaniya in position 5 acid, substituted, at least in position 3 alkoxy group and is responsible mainly the formula IV.

Then, after cooling, if applicable, separate catalytic mass from the reaction medium, for example, by filtering.

In the last step of the method according to the invention are reaction decarboxylation.

To do this, acidifying the resulting liquid by adding a proton acid mineral origin, mainly hydrochloric acid or sulfuric acid to obtain a pH equal to or less than 3, preferably equal to 0-3.

Heat the reaction medium to a temperature, for example in the range of 120-350oC, mainly 150-220oC.

The method is carried out mainly under the autogenous pressure of the reactants.

At the end of the reaction, cool the reaction medium to 20-80oC.

Receive a two-phase medium consisting on the one hand, from the organic phase comprising the formula V, and possibly the original substrate of the formula I, and on the other hand, from the aqueous phase containing the salt.

Separate organic and aqueous phase and Recuperat substituted 4-hydroxybenzaldehyde from the organic phase mainly by distillation.

As mentioned above, the method according to the invention, in particular, is designed to produce vanillin and ethylvanillin.

Below are examples of carrying out the invention. These examples are provided as illustrations and are not restrictive.

Example 1

1. The carboxylation of guaiacolate potassium under pressure of CO2< / BR>
Loaded into the reactor type Barton Corbelin 500 ml of heat-resistant alloy grades B2supplied with blade turbine, 224 g (1,81 mol) of guaiacol.

Add to 31.5 g (228 mol) of potassium carbonate.

Purge the reactor with a stream of CO2. There is a slight evolution of heat.

Heated to 170owithin 7 hours, all the while maintaining the pressure of CO2at 20 bar.

After cooling the reactor to ambient temperature, add 200 ml of water.

Poured a chloride-hydrogen acid 5N. to obtain approximately pH of 7.0. Is rassloennost to pH 1 using chloride-hydrogen acid. Is deposited ortogonalnogo acid.

Separated by filtration. Washed with water and dried the product at 40oC under reduced pressure of 20 mm RT. Art.

Get 38 g ortogonalnogo acid with a concentration of 96 wt.%.

The output is 96% compared to potassium carbonate.

2. Condensation ortovanadata acid/paraformaldehyde

To a suspension of 16.8 g (0.1 mol) ortogonalnogo acid in 16,72 g of water add 14,66 g of 30% aqueous solution of sodium hydroxide (0.11 mol) with stirring and heating.

When the environment becomes uniform, and the temperature reaches 70oC, add 3 g of paraformaldehyde (0.1 mol).

After 6-hour stirring at 70oC carry out a quantitative analysis of the obtained solution purple color using high-performance liquid chromatography.

The results obtained are the following:

- TT (acid ortovanadata) = number of moles converted ortogonalnogo acid to the number of moles introduced ortogonalnogo acid = 42,5%.

- RR (3-methoxy-5-hydroxymethylcellulose acid) = number of moles of the resulting 3-methoxy-5-hydroxymethylcellulose acid to the number of mol is EliLilly to the number of moles converted ortogonalnogo acid = 70,5%.

3. Oxidation

The previous solution was added 1.63 g of 2.5% platinum on coal (0.2 mol.%), then 140 mg of bismuth sulfate (0.2 mol.%).

The temperature was adjusted to 65oC and pH 12, pH support with this value during the reaction by adding 30% hydrate of sodium oxide.

With vigorous stirring in the reactor an oxygen with a rate of 1.5 l/h.

After 3 hours add 0,815 g of platinum on charcoal, and continue the reaction for another three hours.

Then carry out a quantitative analysis of the reaction mixture by high performance liquid chromatography:

- TT (3-methoxy-5-hydroxymethylcellulose acid) = number of moles converted 3-methoxy-5-hydroxymethylcellulose acid to the number of moles introduced 3-methoxy-5-hydroxymethylcellulose acid = 100%.

- RR (5-carboxyaniline) = number of moles of the formed 5-carboxyaniline acid to the number of moles introduced 3-methoxy-5-hydroxymethylcellulose acid = 59%.

4. Decarboxylation

The reaction medium obtained after oxidation, diluted with 100 ml of water, then it is loaded into the reactor type Barton Corbelin of heat-resistant alloy B2. Then pour in 2H. the sulfuric acid solution to obtain LASS="ptx2">

Rapidly cooled by a stream of cold water.

Dilute the reaction mixture with acetonitrile, and then analyzed by high-performance liquid chromatography.

The results obtained are the following:

- TT 5-carboxyaniline = the number of moles converted 5-of carboxyaniline to the number of moles used 5-carboxyaniline = 100%.

- RT vanilla = the number of moles formed of vanilla to the number of moles converted 5-of carboxyaniline = 99,4%.

- RR vanilla/ortovanadata acid = number of moles formed of vanilla to the number of moles used ortogonalnogo acid = 27.4 per cent.

Examples 2-4

Perform a series of tests carboxylation 3-carboxy-4-hydroxy-5-methoxybenzaldehyde.

Loaded into the reactor Barton Corbelin capacity of 50 ml of heat-resistant alloy B2supplied with blade turbine: 0,246 g (1,26 mmol) 5-carboxyaniline and 20 ml of a mixture of acetic acid and water (50/50 in volume) (example 2), 20 ml of water (example 3) and 20 ml of sulfuric acid (5 mmol) (example 4).

Purge the reactor with a stream of nitrogen.

Warm for 20 min at 160oC (examples 2 and 3) and at 200oC (example 4).

Analyze high-performance liquid chrome is the sale of Merck-eluant: 800 ml of H2O/200 ml of CH3CN/3.5 ml of H3PO4- consumption; 1 mlmin-1- detection UV at 240 μm - temperature environment.

The results tabulated.

1. The method of obtaining substituted 4-hydroxybenzaldehyde General formula V

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in which Z1represents an alkoxy radical, a linear or branched, having from 1 to 12 carbon atoms, predominantly from 1 to 4 carbon atoms, such as methoxy radicals, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy;

Z2and Z3identical or different, represent a hydrogen atom or one of the following groups: alkyl radical, linear or branched, having from 1 to 12 carbon atoms, predominantly from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, alkenyl radical, linear or branched, having from 2 to 12 carbon atoms, mostly from 2 to 4 carbon atoms, such as vinyl, allyl; alkoxy radical, a linear or branched, having from 1 to 12 carbon atoms, predominantly from 1 to 4 carbon atoms, such as methoxy radicals, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenyl RA is the emotional connection of General formula I

< / BR>
in which Z1, Z2and Z3have the above values,

in salt form are carboxylation in position 6, to obtain the compounds having the formula II

< / BR>
in which Z1, Z2, Z3have the above meanings;

M is a cation of the metal group (Ia) or a Quaternary ammonium cation,

then carry out a stage of hydroxymethylpropane in position 4, to obtain the compounds having the formula III

< / BR>
in which Z1, Z2, Z3M have the above values,

with subsequent oxidation hydroxymethylene group to the formyl group, to obtain compounds of formula IV

< / BR>
in which Z1, Z2, Z3M have the above values,

and at the last stage decarboxylase compound of formula IV to obtain the desired 4-hydroxybenzaldehyde formula V.

2. The method according to p. 1, characterized in that the use of substituted phenolic compound of the formula I in which Z1represents an alkoxy radical, a linear or branched, having from 1 to 6 carbon atoms, predominantly 1 to 4 carbon atoms, Z2and Z3represent a hydrogen atom.

3. The method according to PP.1 and 2, characterized in that the causesa fact, the carboxylation of substituted phenolic compounds of the formula I is carried out by interaction of the compounds in the form of a salt with carbon dioxide.

5. The method according to p. 4, characterized in that salts of substituted phenolic compounds mainly use salt with metals of group Ia of the Periodic system, mainly sodium and potassium.

6. The method according to p. 4, characterized in that the substituted phenolic compound in salt form is obtained by interaction of the compounds with a base, preferably with sodium hydroxide or potassium, or Quaternary ammonium hydroxide, followed by separation of the resulting water or by reacting with anhydrous carbonate of an alkali metal, preferably with potassium carbonate.

7. The method according to PP.4 to 6, characterized in that the temperature at the stage of carboxylation is 150 - 250oC, mainly 160 - 200oC.

8. The method according to PP. 4 to 7, characterized in that the carboxylation is carried out at pressures of carbon dioxide from atmospheric to 100 bar, mostly 1 - 20 bar.

9. The method according to PP.4 to 8, characterized in that the first stage of the method consists in the cooperation of nameservices carbon.

10. The method of obtaining 2-hydroxybenzoic acid of General formula III

< / BR>
in which Z1, Z2and Z3have the meanings given in paragraph 1;

M denotes a hydrogen atom and/or a cation of a metal of group Ia,

characterized in that the interact 2-hydroxybenzoic acid of General formula II

< / BR>
in which Z1, Z2, Z3and M have the meanings mentioned above,

with formaldehyde or a source of formaldehyde, if necessary, in the presence of a base.

11. The method according to p. 10, wherein the source of formaldehyde is used, trioxane or paraformaldehyde in the form of linear polyformaldehyde with any degree of polymerization, which is mainly the number of links (CH2O) equal to 8 - 100 units.

12. The method according to PP.10 and 11, characterized in that the molar ratio of formaldehyde/salt hydroxybenzoic acid is 0.5 to 3.0.

13. The method according to PP.10 to 12, characterized in that the reaction temperature is 50 - 100oC, mostly 60 - 80oC.

14. The method of obtaining 2-hydroxybenzoic acid of General formula IV

< / BR>
in which Z1, Z2, Z3M have the meanings specified in paragraph 10,

deposits of oxygen or gas, it contains, in an aqueous medium containing an alkaline agent, in the presence of a catalyst based on platinum or palladium, if necessary in the presence of socializaton on the basis of the derived bismuth.

15. The method according to p. 14, characterized in that the catalyst is chosen from the group comprising platinum black, palladium black, platinum oxide, palladium oxide or noble metal deposited on various substrates, such as carbon black, calcium carbonate, activated alumina, or silica, or equivalent substances.

16. The method according to PP.14 and 15, characterized in that the amount of catalyst, based on all of the platinum or palladium, relative to the weight hydroxymatairesinol 2-hydroxybenzoic acid of the formula III is 0.01 - 4% mainly 0.04 to 2%.

17. The method according to PP.14 to 16, characterized in that used as socializaton mineral or organic derivative of bismuth, in which the bismuth atom has an oxidation state greater than 0, for example, equal to 2, 3, 4 or 5.

18. The method according to p. 17, characterized in that the derivative of bismuth is chosen in the group formed by bismuth oxide, bismuth hydroxide, bismuth salts or vesatile with a mineral is the role of bismuth or vesatile mineral oxyacids preferably, sulfite, sulfate, nitrite, nitrate, postitem, phosphate, pyrophosphate, carbonate, perchlorate, antimonate, arsenate, Selenite, selenate, salts of bismuth or vesatile with aliphatic or aromatic organic acids, mainly acetate, propionate, salicylate, benzoate, oxalate, tartrate, lactate, citrate, funatani bismuth or vesatile, mainly gallate, and pyrogallol.

19. The method according to p. 18, characterized in that the derivative of bismuth is chosen from the group formed by: oxides of bismuth Bi2O3and Bi2O4, bismuth hydroxide Bi(OH)3, bismuth chloride BiCl3, bromide bismuth BiBr3, bismuth iodide BiJ3neutral sulfate bismuth Bi2(SO4)3, neutral bismuth nitrate Bi(NO3)35H2O, nitrate vesatile BiO(NO3), carbonate vesatile (BiO)2CO30.5 H2O, bismuth acetate Bi(C2H3O2)3, salicylate vesatile C6H4CO2(BiO)OH.

20. The method according to PP.18 and 19, characterized in that the number of socializaton chosen so that it is brought into the environment, on the one hand, at least 0.1 wt.% metallicheskih the Uta towards hydroxymatairesinol 2-hydroxybenzoic acid of the formula III.

21. The method according to PP.14 to 20, characterized in that the oxidation reaction is carried out in an aqueous medium containing 0.05 to 3 mol of hydroaxe sodium or potassium in relation to hydroxymatairesinol 2-hydroxybenzoic acid of the formula III.

22. The method according to PP.14 to 21, characterized in that the oxidation reaction is carried out at a temperature of 50 - 100oC, mostly 60 - 80oC.

23. The method according to PP.14 to 22, characterized in that the cooled reaction medium and separate the catalyst.

24. The method of obtaining substituted 4-hydroxybenzaldehyde formula V, described in paragraph 1, characterized in that exercise decarboxylation of the acid of formula IV by attaching a proton acid mineral origin, preferably hydrochloric or sulfuric acid to obtain a pH equal to or less than 3.

25. The method according to p. 24, characterized in that the reaction medium is heated at a temperature of 120 - 350oC, preferably at 150 to 220oC and after cooling the separated 4-hydroxybenzaldehyde formula V.

 

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