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    • 专利摘要:
    This is a novel process for the preparation of m-phenoxybenzaldehyde, a useful and valuable intermediate for the synthesis of pyrethroid type pesticides. The process comprises halogenation of m-phenoxytoluene on the side chain, in an inert solvent and in the presence of free radical initiators or strong light to a mixture of the corresponding mono and dihalo derivatives, and conversion of the mixture to m-phenoxybenzaldehyde by a Sommelet-type reaction.
    公开号:SU816397A3
    申请号:SU772522449
    申请日:1977-09-20
    公开日:1981-03-23
    发明作者:Гордон Браун Дейл；Вэйн Брэнд Вильям
    申请人:Американ Цианамид Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF OBTAINING m-PHENOXYBENZAL-DEGIDE
    The invention relates to organic chemistry, specifically to the improvement of the method for producing m-phenoxybenzaldehyde, which is used as a valuable intermediate for the synthesis of pyrethrone type pesticides. A known method for producing aromatic aldehydes-benzaldehyde from a mixture of benzylidene and benzyl chlorides in water, when heated for an hour to 10 ° C, followed by separation by distillation. Yield 93% However, this method, although with a high yield, yielded only the simplest derivative of this range, benzaldehyde. The closest to the technical essence is the method of obtaining m-phenoxybenzyl alcohol, including the direct halogenation of m-phenox toluene under the action of phosphorus halogenides or gsshoidov in the environment of the solvent, such as benzene, mainly at temperatures above 220 ° C, followed by processing a mixture of mono and dihalo derivatives rHjH .-,, -lPHPH O- (O) and (o / O - {o) and acetic acid / sodium with acetic acid, water at reflux, resulting in the formation of a mixture containing m-phenoxybenzaldehyde t2. The disadvantage of this method is the production of m-phenoxybenzaldehyde with admixture of other aromatic derivatives without separation. Furthermore, the method shows that in the first stage, at temperatures below, a strong ring halogenation occurs and the products thus obtained are largely contaminated with undesirable by-products, for example, 3-phenoxy-b-chlorotoluene. In contrast to the effect of PC131, the use of chlorine in the halogenation reaction also leads to significant amounts of undesirable products of mono- and trihalomethyl analogs, and ring halogenation additionally occurs. Thus, conventional halogenation gives a mixture of products, since not all of them can be directly converted into the desired m-feioxibenzaldehyde, the latter is obtained in poor yields and is difficult to isolate in pure form. The purpose of the invention is to increase the yield of m-phenoxybenzaldehyde, as well as the selectivity of the process of its preparation. This goal is achieved by the fact that in the method of obtaining m-phenoxybenzaldehyde, halogenation of m-phenoxytoluene in an inert solvent is carried out at a molar ratio of m-phenoxytrluol and a KWero reagent halogenate of 1: 1.2-2 at the boiling temperature of the reaction mixture in the presence of 0.5 up to 10% by weight of m-phenoxytoluene free radical initiator or in the case of halogenation with chlorine or bromine, the process is carried out under irradiation with a fluorescent lamp, the product obtained by halogenation is treated with hexamethylenetetramino at their molar ratio of 1: 1.2-2 in an aqueous alcohol or an aqueous alkanoic acid, followed by hydrolysis with dilute mineral acid. It is preferable to use carbon tetrachloride as a solvent, bromine with daylight irradiation or sulfuryl chloride with a free radical initiator 2/2-azobis- (2-methylpropionitryl) as the halogenating agent, and hydrochloride or hydrochloride as the mineral acid. acid. Preferably, 2-tert-butylazo-2-cyanopropane or benzoyl peroxide is used as the free radical initiator. The mixture of m-phenoxybenzyl chloride and m-phenoxybenzal chloride can be reacted with 1-2 mol-eq. hexamethylenetetramine in hot aqueous ethanol or hot aqueous acetic acid and the mixture is hydrolyzed with dilute hydrochloric acid. According to the proposed method using from 1.2 to 2 mol-eq. Ha-; The process is carried out in the presence of a free radical initiator or a light source. The conversion of the halogen derivatives of m-phenoxytoluene is carried out under the action of hexamethylenetetramine with hydrolysis with a dilute mineral acid. The proposed method allows m-phenoxytoluene to be halogenated under relatively mild conditions, in an effective solvent for the reactants at a temperature preferably at about the boiling point of the selected solvent. To the reaction mixture, it is advisable to add an effective free radical initiator, for example, lauryl peris, 2,2-azobis- (2-methylpropionitrile), 2-tert-butylazo-2-cyanopropane, benzoyl peroxide, in amounts from 0.1 to 10% by weight. %, and more preferably 1.0 to 10% by weight of m-phenoxytoluene or, instead of an initiator, the reaction mixture can be irradiated with a strong light source, such as a fluorescent lamp, when the halogenating agent is bromine or chlorine. To the specified reaction mixture, the addition of a halogenating agent, for example bromine, chlorine or sulphuryl chloride, in amounts from 1.2 to 2 mol-eq. per mole of m-phenoxytoluene is carried out for a time from 1 to 24 hours or until the reaction is almost complete. The product thus obtained is a mixture of mono- (1I) and dihalo- (III) derivatives of m-phenoxytoluene, containing almost no or containing only a small amount of these unwanted contaminants. This reaction can be schematically written with / Uu-se (vg aai .. / foV fOl (P) x (uHUiiuan op (W) 1) (a, vg eu / ibHtiiu) The halogenation process according to the invention gives relatively mild conditions, the mono- and digald derivatives of formulas II and I, which do not contain contaminants due to impurities of ring-halogenated derivatives of m-phenoxytoluene, can therefore be used without further purification. Example 1. Preparation of m-phenoxybenzaldehyde A. A mixture of m-phenoxytoluene (36.8 g 0.199 mol) and carbon tetrachloride The epipod (150 ml) is boiled under reflux when irradiated with a daylight lamp (250 W) and added dropwise with bromine (64.0 g, 0.400 mol) at such a rate that the color of the reaction mixture is not enhanced, nocjje 4 After boiling, the mixture is concentrated under vacuum and 75 g of Og light brown oil is obtained. The proton NMR spectrum of the oil removed in the SOSC shows the ratio of 9: 1 dibromo derivative (for benzyl npdToaa f 6.55) to monobromo derivative (for benzyl proton d 4,4 ). B. A mixture of mono- and dibromo derivatives (22.5 g), consisting respectively of 20.26 g (0.059 mol) Mi and g (0.00854 mol) II hexamethylenetetramine (19.0 g, 0.135 mol), glacial acetic acid acids (2 ml) and water (27 ml) are heated under reflux for 2 hours, then hydrochloric acid is added and the mixture is heated under reflux for an additional 45 minutes. The reaction mixture is cooled, extracted with ether and the ether extract is shed with diluted acid, alkali, then the magnet is dried over desiccate sulfate, the ether is removed in vacuo and 12.0 g of m-phenoxybenzal dehydride are obtained as a light brown oil; The structure of the compound was confirmed by an NMR spectrum showing the presence of an aldehyde proton (tf 9.95) and aromatic protons (d 7.25 moltlet) in a ratio of 1: 9 (in COCt. In the infrared spectrum a carbonyl group was detected at a frequency of 1680 CM. Example 2 Preparation of m-phenoxybenzaldehyde A. A mixture consisting of m-phenoxytoluene (20.0 g, 0.109 mol), 2,2-azobis-2-methylpropionitrile (AIBN, 1.89 g) and carbon tetrachloride (80 ml) is heated with reflux for more than 1.5 hours, adding dropwise a solution of sulfuryl chloride (22.0 g, O, 163 mol) in tetrachloride carbon (80 ml). The reaction mixture after heating under reflux is then concentrated in a vacuum. 25.8 g of oil are obtained, according to NMR spectroscopy, of 66% monochlor and 29% dichloro derivative. B. A mixture of this oil (14.2 g ), consisting of 9.37 g (0.0357 mol) II and 4.12 g (0, oi2 mol) 1M, is reacted with hexamethylene tetramine (17.1 g) in 60% aqueous ethanol (85 ml) by heating under reflux for 4 hours. The mixture is then cooled, acidified with hydrochloric acid and extracted with ether. The extract is dried over anhydrous magnesium sulphate, concentrated in vacuo, and 10.1 g of the remaining oil is distilled at a temperature of from 120 to laoc (0.05 mm-Hg). 7.5 g of m-phenoxybenzaldehyde ... The aldehyde mass spectrum shows the absence of chlorine in the test product, which indicates the absence of a chlorinated ring during the chlorination stage. Example 3. Analogously to Example 2, but taking 0.1 g (AIBN), instead of 1.89 g, 23.5 g of oil is obtained, which contains 64% monochloro compound and 27% dichloro compound. The oil is then treated as in Example 2 and 6.7 g of m-phenoxybenzaldehyde are obtained. Example 4. Analogously to Example 2, but replacing 60% aqueous ethanol with isoprpranol and dilute hydrochloric acid with propionic acid, 7.2 g of m-phenoxybenzaldehyde are obtained. Example 5. Analogously to Example 2, but adding .17.68 g (0.13 mol) of sulfuryl chloride, instead of 22 g, 6.9 g of m-phenoxybenzaldehyde are obtained. EXAMPLE 6 Analogously to Example 2, with 10.3 g (0.0738 mol) of hexamethylenetetramine (2 mol eq:), instead of 17.1 g, 7.6 g of m-phenoxybenzaldehyde are obtained. Example 7. Analogously to Example 2, but 14.3 g of oil is taken in step C, with a 0.0357 mole of monochloro compound, 0.012 manul of dichloro compound and 6.2 g (0.443 mole, 2 mol eq.) Of hexamethylene tetrahedral. 6.5 g of m-phenoxybenzaldehyde are obtained. Example 8-19. Evaluation of sulphuryl chloride by the ac chlorinating agent for chlorination of the m-phenoxytoluene side chain under various reaction conditions. In the experiments, m-phenoxytoluene, freed from any residual phenolic contamination by pre-washing with alkali and / or filtration through silica gel, was used. To a mixture of m-phenoxytoluene (IV, 5.0 g, 0.024 mol) and 2,2-azobis- (2-methylpropionitrile) AIBN (0.05 g) in carbon tetrachloride (20 ml) is added dropwise sulfuryl chloride (5.45%). g, 0.024 mol), then the solution is boiled under reflux for 18 h, the solvent is removed in vacuo and the residue is analyzed according to (vapor chromatography (PPP) method) using proton NMR spectrum. / or data sources obtained in Table 1. Examples 20-25. Evaluation of chlorine gas as chlorinating agent for chlorine M-phenoxytoluene side chain was irradiated under various reaction conditions. SOLUTOR TEMPERATURE SEE ITEM (i A mixture of m-phenoxytoluene (IV, 5.0 g) of the initiator (if present) and the selected solvent (20 ml) is heated under reflux, then through chlorine gas is bubbled through it. At the end of chlorine flow, the reaction mixture is heated under reflux for 18 hours before sampling. After this time, the selected samples are evaporated in vacuo. The percentage composition is then determined by the PFC and NMR method. PFC analysis in a column of 85 x 0.6 dtf. outer diameter) with a carrier of 10% OU-17 for gas-chromium at. The delay time is as follows min: IV 2.4, II 8.0, III 12.4, J 5.6. The structure of compound V is consistent with the mass spectrum and NMR spectrum. Chemical proton displacement of NIR for compounds II, III, IV and V (cG, LAD): II 4.45, III 6.57, IV 2.25., V 2.2 -2.3 Example 26. Evaluation of light-initiated chlorination of m-phenoxytoluene in carbon tetrachloride by boiling with reflux cooling using chlorine gas as a chlorinating agent. A solution of m-phenoxytoluene (38.5 g, 0.21 mol) is heated in reverse. a refrigerator, irradiated with a daylight lamp (275 W), then gaseous chlorine is introduced into the boiling solution and various intervals, interrupting the reaction, samples were taken for analysis by vapor phase chromatography. At this time, the weight of chlorine coming from the calibrated cylinder is recorded, with some of its loss being recorded. -PFC data (6-foot glass column, 1/4 inner diameter, 3% OU-17 carrier, temperature is given in Table 3. After 34 g of chlorine is introduced, the reaction mixture is cooled, evaporated
    ten
    8AIBN
    9AIBN 12 / AIB 13.AIB 14.AIB 15. AIB
    75-80
    Chlorination
    Ring rings
    IV-6% MonoCl.
    Boiling Chlororovachlor 5 9% c reverse CH Dichloro with a 35% condenser under vacuum and obtain 40.3 g of orange oil. His analysis, by NMR spectroscopy, shows the following composition, wt.%: IV 4,5,11 52,0,111 43,5. These data refer to 16.5 g of 34 g of chlorine used in the reaction. As shown by examples 20-25, both analytical methods confirm the low level of ring chlorination (less than 5%). An example. Preparation of c-dianobenzyl esters by the reaction of m-phenoxybenzaldehyde with acid chlorides in the presence of alkaline cyanide. A mixture of 0.05 gm mol of m-phenoxybenzaldehyde and 0.05 gm mol of acid chloride 3, .3-dimethylspiro (cyclopropan-1, 1 -indenden) -2-carboxylic acid is slowly added in portions to the solution. A mole of cyanide in 100 ml of water is added, then it is stirred for 1.5 hours at and extracted with three 50 ml portions of ether. The extracts were washed with 10% hydrochloric acid, saturated sodium bicarbonate solution, water, dried over sodium sulfate, and then the ether was removed in vacuo to give 3,3-dimethylspiro (cyclopropane-1, 1 - in the residue of oC-cyano m-phenoxybenzyl). indene) -2-carboxylate as a yellow-brown oil. ; Table IV 4% Mnochlor 61%. Dichlorum 35% IV 4% Monochlorum Dichlorine Chlorination Ring ring chlorination 51% Monochlorine Chlorination of CH, Chlorination Chlorination of the ring, ring of chlorination Chlorination of the ring
    CCIj Boiling with
    Not
    ten
    CC1. Also
    Continued table. one
    T a b l n c a 2 reflux condenser
    权利要求:
    Claims (4)
    [1]
    Main product: W slightly formed trichloromethyl. Invention 1. Method for preparing m-phenoxybenz (L-dehydate by halogenating m-phenoxy-fluorol in an inert dissolving medium L when heated, followed by acid hydrolysis, about tl and-h and fa. And that, in order to increase the yield of the target product and the selectivity of the process, the halogenation is carried out at a molar ratio of m-FeOoxytoluene and halogenating reagent of 1: 1.2-2 at boiling points of the reaction mixture in the presence of 8II from 0.5 to 10% by weight from m-fenok sitoluene the free radical initiator or in the case of halogenation with chlorine or bromine, the process is carried out under irradiation with a fluorescent lamp, the product obtained by halogenation is treated with hexamethylenetetramine at their molar ratio 111.2-2, Q in aqueous C alcohol, C or aqueous alkanoic acid, followed by hydrolysis mixtures of dilute mineral acid.
    [2]
    2. The method according to p. 1, about tl and h ay1D and and g by the fact that carbon tetrachloride is used as an inert solvent,
    Table 3 of the halogenated agent — the broadening is carried out by irradiation with a fluorescent lamp, and hydrochloric acid is used as the mineral acid.
    [3]
    3. The method according to claim 1, characterized in that sulphuryl chloride is used as a halogenating agent, and 2,2-azobis- (2-methylpropionitrile) is used as a free radical initiator, in an amount from 0.5 to 10% by weight of m-phenoxytoluene, hydrochloric acid is used as a mineral acid.
    [4]
    4. A method according to claim 1, characterized in that 2-tert-butyl-2-cyanopropane or benzoyl peroxide in an amount of from 0.5 to 10% by weight of m-phenoxytoluene is used as the free radical initiator. Sources of information taken into account in the examination 1.Bibman B.Ya., Ignatov M.A., Vershinin P.V. Parfenov A.I., Annenkova E.I., Nuikin I.V. and Denisov M.I. Getting Benzaldehyde. - Journal of Applied Chemistry, 38, 7 ,, 1669, 1966. 2. The patent of Belgium 809867, cl. S. 03 C, published. 1974 (prototype).
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    同族专利:
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    PL200964A1|1978-07-31|
    ATA677677A|1979-04-15|
    AU512709B2|1980-10-23|
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    引用文献:
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    法律状态:
    优先权:
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    US05/726,017|US4108904A|1976-09-22|1976-09-22|Process for the preparation of m-phenoxybenzaldehyde|
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