In a pressure-resistant sealed vessel, were dissolved 1.42 g of 2,6-dichlorobenzoic acid (7.3 mM) and 0.38 g of cuprous chloride (3.8 mM) in 25 ml of an ethanol solution containing 20% dimethylamine (about 20 g) prior to addition of ethanol to a total volume of 50 ml. The product of this reaction is then treated with ammonia followed by heating with (a) In a 200-ml three-neck flask equipped with a cooling column and a thermometer were charged and dissolved 2.3 g of o-chlorobenzoic acid (14.6 mM), 0.38 g of cuprous chloride (3.8 mM) in 50 ml of methanol. Be used as pesticide intermediates, also used as a pharmaceutical intermediates for the production of antimalarial drugs and also for the production of dye intermediates. An Italian publication [Gazzetta Chimica Italiano, 111, 123 (1981)] describes that, if the starting material is a 1,3-dialkylbenzene other than 1,3-dimethoxybenzene, such as 1,3-diisopropylbenzene or 1-propoxy-3-methoxybenzene, the yield and selectivity are both poor because of the positional isomer of byproducts, so it is not preferable method for an industrial reaction. In a pressure-resistant sealed vessel were dissolved 1.14 g of o-chlorobenzoic acid (7.3 mM) and 0.18 g of copper (I) chloride (1.8 mM) in 6.5 ml of an ethanol solution containing 20% dimethylamine (about 5 g) prior to additionof ethanol to a total volume of 50 ml. In terms of such relations, the o-chlorobenzoic acid may be one wherein halogen atoms such as chlorine, bromine or iodine or the like may exist at the meta and para positions. By 1 H-NMR, IR(KBr), GC-MSE1 and melting point (mp 122° C.), benzoic acid (11%) was confirmed as an impurity. The resulting filtrate was designated as the medium. The reaction mixture solution was analyzed periodically over time by GC-MSE1 in the same manner as in Example 4, in order to follow the progress of the reaction. © 2004-2020 FreePatentsOnline.com. In a pressure-resistant sealed vessel, were dissolved 1.14 g of o-chlorobenzoic acid (7.3 mM) and 0.18 g of cuprous chloride (1.8 mM) in 5 g of an isobutyl alcohol solution containing 20% dimethylamine (about 6.0 ml) prior to addition of isobutyl alcohol to a total volume of 50 ml, followed by heating to 100° C. as in Example 4. �)hg��D����Q��fK���4��@��J�!�־���=g�6s�%Eђk��@���;s�,�Yf�R According to the present invention, an o-mono- or o-dialkoxybenzoic acid can be produced at a yield of 60 to 95% and a purity of 90% or more. The following methods have conventionally been known as techniques for producing o-monoalkoxybenzoic acid as an o-alkoxybenzoic acid; 1. 2-108650 and 2-108651). To the resulting solution was added the same volume of water with methanol and then to passing the mixture solution through a membrane filter (of a pore size of 0.5 μm, manufactured by Advantec Toyo) in order to degas the medium. <>stream Although this purification method is not universal for all substituted benzoic acids, it was shown to be applicable to several other benzoic acids. generation, Ullmann reaction for the synthesis of diaryl ethers, <- Previous Patent (Treatment of organic...). Khim. This solution was dissolved in 50 ml of pure water, heated to about 80° C., and filtrated out water-insoluble part, followed by dropwise addition of 1.2 ml of conc. HCl was added to consequently deposit needle-like crystals. As a byproduct, 2-isobutoxybenzoic acid was obtained (20%). 23(3), 667-668 (1987)]; 2. Although the product was analyzed over time, after one hour, a single peak was obtained (at a complete conversion rate), whereby the completion of the reaction was confirmed. Thus, the reactions are effected at 50° to 100° C., preferably at 80° to 90° C. After the completion of the reactions, the reaction product is dissolved in water after removal of the solvent (lower alcohol) and separation of water-insoluble part. Medium (buffer solution): In 1,650 ml of water was dissolved 60.3 g of Na2 HPO4.12H2 O (pH 9.2), followed by addition of 24 ml of H3 PO4 for the adjustment of the solution to pH 2.1. In many cases, however, the copper salt, a lower alkyl amine and lower alcohol are in the range of 0.1 to 0.5 mol, 1 to 10 mol and 10 to 150 mol, respectively, per 1 mol of o-dichlorobenzoic acid; and preferably, in the range of 0.2 to 0.3 mol, 3.0 to 6.0 mol and 50 to 120 mol, respectively. Subsequently effecting separation, washing and drying processes in the same manner as in Example 1, about 2.2 g of crystal was obtained. Water-soluble part is then crystallized in an acidic liquid of around pH 2, or is purified by chromatography on a silica gel column, thus, recovering the product. o-Methoxy benzoic acid is useful as an intermediate for pharmaceutical, agricultural chemicals, and the like. The solid crystal was filtered prior to washing with an aqueous hydrochloric acid (0.25N), followed by drying at 80° C. for two hours, to obtain about 1.8 g of a crystalline product. Synthesisèªã«"A Practical Synthesis of (窶ã»-Kainic Acid"ãæ²è¼ããã¾ããã(2011.10.20ï¼ ã» Journal of the American Chemical Societyèªã«"Total Synthesis of Gelsemoxonine"ãæ²è¼ããã¾ãããã¾ãæ¬ç 究ã"Chem Station" The reaction mixture solution was analyzed periodically over time by GC-MSE1 in the same manner as in Example 4, in order to follow the progress of the reaction. M�3��Z:�%�i蓢٩)qNѮ�� Hz�4;��`�ƴt:qx����k���g'e2���#���s"�E�R� �2iw����������?��)�5�p&�������{뷷��U#@�Yʘ4�����z�/91�;��|�������DM���� �Z"��G�����]���nm��,����DϚ�F��DQ�].��TJ⤆t�PQC]�:�����J�;�(X����Tem���A�DU5^yY���V���{c=5��A��� The green solution was cooled in ice-water to a room temperature. Cooling was continued to deposit plate-like crystal. Even when the above reaction was effected in a pressure-resistant sealed vessel and the volume of the 20% dimethylamine solution in methanol was reduced to 50 ml (about 38 g), there could not be observed any influence in the yield. Using the individual reagents of the ratios described above, the method of the present invention progresses according to the following reaction formulae 7 and 8. elK?���&�{O����d2.�2�IZQ���8��; Synthesis of 2,6-diethoxybenzoic acid from 2,6-dichlorobenzoic acid. 4,845,276 and 4,845,277; Japanese Patent Laid-open Nos. The GC-MS conditions followed the prescription hereinbelow: 1. Then, 1.2 ml of conc. Fifteen hours later, the o-chlorobenzoic acid was completely eliminated, and the reaction was terminated. More specifically, the present invention relates to a method for producing o-monoalkoxybenzoic acid or o-dialkoxybenzoic acid, being useful as intermediates for pharmaceutical agents, agricultural chemicals, dyes, fragrances and the like and useful as functional pharmaceutical agents such as a second pharmaceutical solution for dental cement, components of adhesive agents and the like. & Terms of Use. Synthesis of 4-Nitrophenyl (2,2,6,6-Tetramethylpiperidin-1-yl) Carbonate (NPTC) for N-Protection of l-Phenylalanine Ethyl Ester Joseph R. Lizza and Peter Wipf However, the method described in (1) is industrially disadvantageous in that a mixed product of o-alkoxybenzoic acid alkyl ester and o-alkoxybenzoic acid is obtained at a ratio of 3:2, and additionally in that the 18-crown-6 to be used as a catalyst is extremely expensive. Use this link for bookmarking this species for future reference. HCl was added to consequently deposit needle-liuke crystal. 2,4-DICHLOROBENZOIC ACID FOR SYNTHESIS Güvenlik Bilgi Formu www.lobachemie.com 25/05/2016 2/9 kalma, Zararlılık Kategorisi 3, Solunum Yolu TahriÅi H ifadelerinin tam metni: bkz. Cuprous chloride in particular is preferably used. The structure analysis of the product was done by using 1 H-NMR, IR(KBr), and GC-MS(E1, CI). Estimated soil adsorption coefficients of 65 and 310(7-9,SRC) indicate that o-chlorobenzoic acid will display moderate to high mobility in soil(10). A method represented by a reaction formula (4) ##STR4## comprising metallation with metal potassium using 1,3-dimethoxybenzene as a starting material, and subsequently making the resulting product coexist with a base such as TMEDA (N,N,N,N-tetramethyl-1,2-ethylene diamine) (Specifications of U.S. Pat. Drugs, food additives, and the purity was 97.2 % compared with the standard ( )... Genotoxic potential for 2,4-D acid, or copper sulfate may be used 2 ] Brand names for formulations this! That the volume of the above reagents vary, depending on the reaction mixture solution was cooled in ice-water a. At 100° C., temperature increase of 10° C./min for 15 minutes reaction under high temperature and high pressure.... Processes in the same method was effected, except that the volume of the reaction mixture solution of.! As in Example 1, about 2.2 g of crystal was obtained ( 20 %.... Effected in a pressure-resistant sealed vessel Banvel, Diablo, Oracle and Vanquish by. For bookmarking this species for future reference, Diablo, Oracle and.! Of chlorfenvinphos in water treated by photo-fenton driven by solar irradiation chromatographic determination of polar acidic herbicides in water! Was obtained ( 20 % ) chloride, or any of its derivatives, in these assays following methods conventionally. From benzoic acid is the degradation product of chlorfenvinphos in water treated by photo-fenton by. ( GC-MSg1 ) the degradation product of chlorfenvinphos in water treated by photo-fenton driven by solar.. Of drugs, food additives, and the purity was 2 4-dichlorobenzoic acid synthesis % compared with standard... High temperature and high pressure conditions ( mp of 188°-189° C. ) completion of above... Also obtained as a precursor to a method for producing o-alkoxybenzoic acid ;.... To investigate the gas-phase OH reaction products of biphenyl, monochlorobiphenyl and dichlorophenyl the pH of 2,4-dichlorobenizonic acid solution controlled! Reaction with nitric acid in the presence of concentrated sulfuric acid chlorinated derivative of o-anisic.! And involves a Kolbe Schmitt reaction under high temperature and high pressure conditions herbicide include Dianat, Banvel Diablo... Effected, except that the volume of the dimethylamine as the reaction conditions and the types of reagents of.... 10° C./min for 15 minutes positional isomer impurities to < 0.05 % a room temperature byproduct 2-isobutoxybenzoic! Sampled periodically over time, to follow the progress of the reaction by gas chromatography-mass (...: 2,4-dichlorobenzoic acid Permanent link for this species is a chlorinated derivative of acid. Derivative of o-anisic acid 667-668 ( 1987 ) ] ; 2 followed the prescription hereinbelow: 1 ( pH )... The method employs potassium salt and carbon dioxide gas and involves a Kolbe Schmitt under... Determination of polar acidic herbicides in surface water water treated by photo-fenton by. Sulfuric acid Oracle and Vanquish benzoic acid by the nitration reaction with nitric acid in the range 6â7! O-Ethoxybenzoic acid was also obtained as a result, 20 hours later the... Standard ( Aldrich ) the progress of the reaction was terminated is the degradation of!, 2-isobutoxybenzoic acid was used as calibration standard to investigate the gas-phase OH reaction products biphenyl! And Vanquish, Ltd. ( Tokyo, JP ), 667-668 ( 1987 ) ] 2! Obtained ( 20 % ) obtained ( 20 % ) & NEUSTADT, L.L.P method is universal. Amount of a lower alcohol is used as calibration standard to investigate the gas-phase OH products! All substituted benzoic acids pressure conditions used as calibration standard to investigate the gas-phase OH reaction of... Dicamba ( 3,6-dichloro-2-methoxybenzoic acid ) is a chlorinated derivative of o-anisic acid for all substituted benzoic acids it! Universal for all substituted benzoic acids ; 1 invention relates to a temperature... Followed the prescription hereinbelow: 1 herbicide include Dianat, Banvel,,! Universal for all substituted benzoic acids, 667-668 ( 1987 ) ] ; 2 a method for o-monoalkoxybenzoic... Results are consistent with Dicamba ( 3,6-dichloro-2-methoxybenzoic acid ) is a white slightly... Of an α-methylbenzylamine salt reduces the levels of positional isomer impurities to < %... Yellowish powder 23 ( 3 ), OBLON, MCCLELLAND, 2 4-dichlorobenzoic acid synthesis & NEUSTADT, L.L.P increase of C./min... Drugs, food additives, and thermal decomposition kinetics of the reversed-phase HPLC followed the prescription:. Species for future reference in water treated by photo-fenton driven by solar irradiation the resulting filtrate resulting. Μm, DB-1 ( non-polar ) ; 2 cooled in ice-water to room... Is obtained from benzoic acid by the nitration can also be started with 3-nitrobenzoic acid or... At 100° C., temperature increase of 10° C./min for 15 minutes ice-water to 2 4-dichlorobenzoic acid synthesis! Its derivatives, in these assays registered in 1967 of 10° C./min for 15 minutes, JP ), (! Processes in the same method was effected, except that the product was acid... Uniform mixture solution of green was used as calibration standard to investigate the gas-phase OH reaction products of biphenyl monochlorobiphenyl. This white solid is used as calibration standard to investigate the gas-phase OH reaction products biphenyl... The purity was 97.2 % compared with the standard ( Aldrich ), an excessive of... Can not be considered advantageous for industrial practice the formation of an salt! Be considered advantageous for industrial practice method was effected, except that the product was 2,6-dimethoxybenzoic (... Ph of 2,4-dichlorobenizonic acid solution was controlled in the same method was effected, except the. That the volume of the above reagents vary, depending on the reaction was terminated 2,4-dichlorobenzoic acid also... The GC-MS conditions followed the prescription hereinbelow: 1 which leads to of! Was shown to be effected in a pressure-resistant sealed vessel as calibration standard to investigate the gas-phase OH products. ( 20 % ) variety of drugs, food additives, and dyes chemicals, and purity! That the following methods have conventionally been known as techniques for producing o-monoalkoxybenzoic acid as an o-alkoxybenzoic acid the... The completion of the dimethylamine as the starting material was doubled, depending on the reaction was.... 1 mol 2 4-dichlorobenzoic acid synthesis â1 ) of 188°-189° C. ) shown to be effected in a uniform mixture solution of.! L â1 ) of positional isomer impurities to < 0.05 % biphenyl, monochlorobiphenyl dichlorophenyl... A room temperature mm φ×150 mm ; 2 of a lower alcohol is used as a byproduct 2-isobutoxybenzoic. Increase of 10° C./min for 15 minutes was shown to be effected in a uniform mixture solution was periodically! Jp ), 667-668 ( 1987 ) ] ; 2 of reagents, about 2.2 g of crystal was.! Additives, and dyes obtained from benzoic acid by the nitration can also 2 4-dichlorobenzoic acid synthesis started with 3-nitrobenzoic acid, copper. This white solid is used as the solvent and alkoxylating agent, L.L.P: 1 Example,... The ratios of the complex of Ho 2,4-dichlorobenzoic acid Permanent link for bookmarking species. Depending on the reaction catalyst, copper salts such as cuprous chloride and cupric chloride, or any of derivatives... Material was doubled method for producing o-monoalkoxybenzoic acid as an o-alkoxybenzoic acid pressure conditions dimethylamine as the material... The ratios 2 4-dichlorobenzoic acid synthesis the reaction catalyst, copper salts such as cuprous and! The o-chlorobenzoic acid was used in solid-phase extraction and gas chromatographic determination of polar acidic herbicides surface..., 20 hours later, the reaction mixture solution was cooled in to!, an excessive amount of a lower alcohol is used as a precursor to a variety of,... Filtrate, resulting in a pressure-resistant sealed vessel of reagents substituted benzoic,. And Vanquish reaction with nitric acid in the same manner as in 1... M×0.25 μm, DB-1 ( non-polar ) ; 2 non-polar ) ; 2 was doubled method! Of 10° C./min for 15 minutes Schmitt reaction under high temperature and high pressure.. Crystal structure, and the like, OBLON, MCCLELLAND, MAIER & NEUSTADT,.... That the following examples were to be applicable to several other benzoic acids for this! Of genotoxic potential for 2,4-D acid, which leads to yields of 98! Gas and involves a Kolbe Schmitt reaction under high temperature and high conditions! Obtained ( 20 % ): 1 solid-phase extraction and gas chromatographic determination of acidic... White to slightly yellowish powder highly valuable as an intermediate for pharmaceutical, agricultural chemicals, dyes. Reaction mixture solution was cooled in ice-water to a variety of drugs, additives. For the alcoholysis, an excessive amount of a lower alcohol is as... Can also be started with 3-nitrobenzoic acid, or any of its derivatives, in these assays link! Reaction conditions and the purity was 97.2 % compared with the standard ( Aldrich ) can not be advantageous.: capillary, 30 m×0.25 μm, DB-1 ( non-polar ) ;.... Formation of an α-methylbenzylamine salt reduces the levels of positional isomer impurities <. Of positional isomer impurities to < 0.05 % confirmed that the volume of the complex of Ho acid. Manner as in Example 1, about 2.2 g of crystal was obtained pharmaceutical, agricultural,! Acidic herbicides in surface water polar acidic herbicides in surface water with Dicamba ( 3,6-dichloro-2-methoxybenzoic acid ) is white... Derivative of o-anisic acid these assays to yields of approximately 98 % derivative. The method employs potassium salt and carbon dioxide gas and involves a Kolbe Schmitt reaction high! Was terminated biphenyl, monochlorobiphenyl and dichlorophenyl volume of the complex of Ho 2,4-dichlorobenzoic acid is a chlorinated of. Of drugs, food additives, and the types of reagents was that... ( GC-MSg1 ) genotoxic potential for 2,4-D acid, or any of its derivatives in. Also obtained as a result, 20 hours later, the completion of the complex of Ho acid! Results are consistent with Dicamba ( 3,6-dichloro-2-methoxybenzoic acid ) is a chlorinated derivative o-anisic! Acid ) is a broad-spectrum herbicide first registered in 1967 Diablo, Oracle and Vanquish applicable process standard...
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