Structure of 2,3-Dimethylchlorobenzene
CAS No.: 608-23-1
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CAS No. : | 608-23-1 |
Formula : | C8H9Cl |
M.W : | 140.61 |
SMILES Code : | CC1=CC=CC(Cl)=C1C |
MDL No. : | MFCD00060689 |
InChI Key : | NVLHGZIXTRYOKT-UHFFFAOYSA-N |
Pubchem ID : | 32884 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H227-H315-H319 |
Precautionary Statements: | P210-P264-P280-P302+P352+P332+P313+P362+P364-P305+P351+P338+P337+P313-P370+P378-P403+P235-P501 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxygen; In acetic acid; xylene; at 35 - 40℃;Purification / work up; | Other experiments were carried out on actual oxidation mixtures from reactions of 3- and 4-chloroxylene with oxygen in acetic acid in the presence of a catalyst. In some cases the catalyst components were removed by precipitation, for example with oxalic acid, but the low levels of metals present in those samples still containing catalyst components did not affect the solubility characteristics of the organic species. At least a portion of oxidation reaction mixture was distilled in vacuo to remove acetic acid, leaving a solid residue which was dissolved in water. The extraction of a 30 wt. percent aqueous solution of 3- and 4-chloroxylene oxidation mixture was carried out with xylene. Six extractions were made starting with 130 kilograms (kg.) of solution extracting the aqueous phase with 155 kg. of xylene. At the beginning the temperature was approximately 35 C., and later was raised to 40 C. to present the crystallization of chlorophthalic acid. The results of extraction are shown Table 5. Unless noted, the values in the table represent relative percentages in the composition of the designated components (total percentage equals 100percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxygen; acetic acid;cobalt(II) acetate; manganese(II) acetate; sodium bromide; at 152 - 190℃; under 14251.4 Torr; for 0.5 - 2h;Product distribution / selectivity; | A 3.5 liter reaction vessel equipped as described above was charged with a 95:5 mixture of 4-chloro-o-xylene and 3-chloro-o-xylene (492.1 g, 3.50 mol), acetic acid (1925 mL, 32.06 mol), cobaltous acetate tetrahydrate (13.1 g, 0.0526 mol, 1.50 mole % based on 3.5 moles of 3- and 4-chloro-o-xylene), manganous acetate tetrahydrate (6.4 g, 0.0261 mol, 0.75 mole % based on 3.5 moles of 3- and 4-chloro-o-xylene), sodium bromide (0.6 g, 0.0060 mol, 0.17 mole % based on 3.5 moles of 3- and 4-chloro-o-xylene), and sodium acetate (2.9 g, 0.0354 mol, 1.01 mole % based on 3.5 moles of 3- and 4-chloro-o-xylene). The reaction vessel was sealed and pressurized with nitrogen to 19 bar and then heated to about 160 C. Compressed air was then introduced into the reaction mixture at a rate such that the concentration of oxygen in the gas emerging from the reactor gas outlet valve was about 0.5%. The reaction temperature was maintained at about 160 C. for 1 hour and was then raised to about 175 C. and was maintained at that temperature until ?oxygen breakthrough? was noted. Oxygen breakthrough marked the beginning of the post-oxidation phase of the reaction. The compressed air being fed to the reactor was then diluted with sufficient nitrogen to limit the concentration of oxygen in the gas emerging from the reactor gas outlet valve to less than about 2% . The reaction temperature was raised to about 190 C. and maintained at that temperature throughout the post-oxidation phase which lasted approximately three hours. The reaction mixture was then assayed by HPLC and GC and found to contain the product diacids as a mixture of 3-chlorophthalic acid and 4-chlrorophthalic acid containing less than 10,000 ppm chlorobenzoic acids. Conversion of starting material to products was in excess of 90 percent. Examples 2-14 Data for a series of oxidation reactions conducted as described in Example 1 together with modifications to reaction parameters indicated are gathered in Table 1. The data demonstrate the effectiveness of the method of the present invention to produce high yields of chlorophthalic acid while limiting the amount of chlorobenzoic acid by-products. In Table 1 the header ?Variation? refers to the reaction parameter being varied in the Example, ?standard? refers to the amounts of reagents and reaction conditions used in Example 2 which are given below. 19 barabs nitrogen pressure, stirrer speed 800 rpm. Temperature 152 C. at initial oxygen introduction. Cooling begun immediately upon reaction initiation to maintain an internal temperature of about 160 C. After 60 min the temperature was raised to 175 C. At the beginning of the post-oxidation phase of the reaction the temperature was raised to 190 C for a period of 60 minutes. Still referring to Table 1, the term ?air input? refers to the variation in which the reaction was ?oxygen limited? meaning that the gas flow rate was initially 900 l/h (scaled value 180 l/h), much slower at the end of the reaction (?EOR?). The heading ?Oxidation Conds.? refers to the conditions employed in the oxidation reaction which were either (1) the ?standard? conditions as given for Example 2 or the ?oxygen limited? reaction conditions of Examples 4 and 5. The heading ?Post-Oxidation Conds.? refers to the duration (time) and temperature of the reaction following ?oxygen breakthrough?. The heading ?Cl-phthalic acid? refers to the total amount of 3- and 4-chlorophthalic acid present in the crude product mixture at the end of the oxidation reaction. The values given in the column headed ?Cl-phthalic acid? are the combined ?area percent? of the peaks attributed to 3- and 4-chlorophthalic acid in a gas chromatogram of the crude product mixture. The heading ?Isomeric CIBA's? refers to the total amount of 2-, 3-, and 4-chlorobenzoic acids present in the crude reaction mixture and expressed in parts per million (ppm). 2-chlorobenzoic acid, 3-chlorobenzoic acid, and 4-chlorobenzoic acid are believed to arise by decarboxylation of 3-chlorophthalic acid and 4-chlorophthalic acid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Under the protection of nitrogen, added in a reaction bottle 24 g mgnesium filings (1mol) and 160 ml of tetrahydrofuran, under stirring at room temperature is dropped to 18.5 g 2,3-dimethyl-chlorobenzene (0.1mol) and 100 ml of a mixed solution of tetrahydrofuran, initiate the reaction, and then to continue dropping 166.5 g 2,3-dimethyl-chlorobenzene (0.9mol) and 1000 ml of a mixed solution of tetrahydrofuran, completion of the dropping, reflux reaction 5 hours. With ice-bath cooling the resulting Grignard reagent, dropping 73 g N, N-dimethyl formamide (1.0mol) and 300 ml of a mixed solution of tetrahydrofuran, controlling the reaction temperature is not higher than 30 degrees, the dropping to the reaction at room temperature 5 hours. Reaction of adding the end of 1000 ml of saturated ammonium chloride solution to hydrolyze 1 hour, the organic phase is separated, the aqueous phase is extracted with ethyl acetate once, combined with the phase, using 500 ml saturated salt water washing, layering, organic phase with 50g mixing and drying by anhydrous sodium sulfate 1 hour, filtered, filtrate concentrated to dry, is 2,3-dimethoxy benzaldehyde, the yield is 82percent, the purity of 85percent. |
Tags: 608-23-1 synthesis path| 608-23-1 SDS| 608-23-1 COA| 608-23-1 purity| 608-23-1 application| 608-23-1 NMR| 608-23-1 COA| 608-23-1 structure
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