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    • 专利摘要:
    1426000 Alkyl trans-chrysanthemates SUMITOMO CHEMICAL CO Ltd 14 May 1973 [16 May 1972 18 May 1972 5 June 1972 1 March 1973] 22869/73 Heading C2C [Also in Division B1] Alkyl trans-chrysanthemate compounds are prepared by contacting the corresponding cisisomer or a mixture thereof with the trans-isomer with a catalyst which is an alkali metal catalyst, an alkali metal hydride catalyst or an alkaline catalyst prepared by reacting an alkali metal, an alkali metal hydroxide and an alumina by heating at a temperature which exceeds the melting point of the alkali metal. The resulting ester may be hydrolysed to the corresponding acid.
    公开号:SU929007A3
    申请号:SU731922039
    申请日:1973-05-15
    公开日:1982-05-15
    发明作者:Нагаси Цунеюки；Сузукамо Гоху；Енеоси Юкио；Есиока Хиросуке
    申请人:Сумитомо Кемикал Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    39 carbon with better yield at lower quantitative consumption of alkaline catalyst. This goal is achieved by using metal or molten or dispersed potassium, or sodium, or their hydroxides, or their mixture dispersed on alumina at the atomic or molar ratios,: NaOH or KOH, as an alkaline catalyst in the isomerization process. : K or Na, equal to 1: 0.025-0.5: 0, 05-0.5; or A1 (0, or .Na, equal to 1: 0.08-0.5: 0.09-0.7, or alkali metal hydride in the amount of 0.001-0.5 mol per mole of the initial AIS-isomer, and isomerization lead at 50-180 ° C. It is advisable to carry out the process in an inert solvent. A mixture of cis and TPdHc isomers is used as the starting product. In addition, alumina used in some cases should have a well-developed surface, i.e. 25 m / t. Preparation of catalytic systems is shown in Examples A to P. The amount of catalyst is usually in the range of 0.01 to 0.2 mol per mole. o 11, is-isomer. The reaction can be carried out quantitatively without using a solvent. If necessary, an inert aliphatic solvent, for example hexane, heptane, isopentane, decahydronaphthalene or dodecane, or an aromatic hydrocarbon, for example benzene, toluene, xylene, or ether, for example tetrahydrofuran can be used or dioxane: For safe and continuous isomerization, the reaction is preferably carried out under an inert gas atmosphere. Before contacting the applied and is-isomer with the catalyst, it is advisable to dry it. Conventional drying agents like alumina or silica gel can be used to separate the water from the starting product. The reaction time depends on the amount of catalyst used and on the reaction temperature. In general, at higher temperatures, the reaction time is shorter. If the reaction is carried out within the specified region of the reaction temperature, it is not necessary to strictly control the reaction time. The progress of the isomerization reaction can be monitored in a known manner, for example, by gas chromatography or infrared spectroscopy. After complete isomerization, the catalyst is isolated from the reaction mixture by conventional means, for example by filtration. After that, the product is subjected to purification, for example distillation. An alkyl trans-chrysanthema is obtained. It is also possible to treat the reaction mixture first with water, alcohol or an alkaline solution, without providing a catalyst. After this, alkyl-trins-chrysanthemate can, if necessary, be subjected to hydrolysis to produce free trs (IC-chrysanthemic acid. Preparation of the catalyst by dispersing alkali metal on a carrier, Example A. A. A 200 ml flask is charged with 100 g of alumina calcined beforehand for 2 hours at, aluminum oxide is heated under nitrogen atmosphere with stirring. 10 g of sodium metal is added and the mixture is stirred at this temperature for 2 hours. A catalyst is obtained. Example B. According to Example A, I get t catalyst of 100 g of alumina and 5 g of metallic sodium, Example B. According to example A, a catalyst is obtained from 100 g of alumina and k g of metallic potassium, Example D, a 200 ml flask with a capacity of 200 ml is loaded with 100 g of alumina previously calcined for 2 hours at 500 ° C. Alumina is heated under nitrogen to 200 ° C. with stirring. 10 g of sodium metal is added. The mixture is stirred at this temperature for 1 hour. Example D, According to Example G, a catalyst is obtained from 100 g of alumina and 10 g of metallic potassium, Example E, According to Example G, a catalyst is obtained from 100 g of silica gel and 7 g of metallic sodium. Obtaining a catalyst from an alkali metal, its hydroxide and alumina. Example G. In a flask of capacity 200 ml load 100 g of alumina and, stirring, heated to 00 ° C. Then, under nitrogen atmosphere, 12.0 g of sodium hydroxide is charged, stirring the mixture for 1 hour. At the same temperature, 5 g of metallic sodium are then added, stirring the mixture for 2 hours. The mixture is then cooled. Get the mash with a molar ratio of AlnOj:: NaOH: Na 1: 0, 2205. Example 3. According to Example G, a catalyst is obtained from 100 g of alumina, 2.0 g of sodium hydroxide and 10.0 g of metallic sodium. The molar ratio of A1 rj) o: NaOH: Na 1:: 0.051: 0 ,. Example I. According to Example G, a catalyst is obtained from 100 g of aluminum oxide, 1.0 g of sodium hydroxide, and 10.0 g of metallic sodium. The molar ratio of Aco,: MaOH: Na 1: 0,0257: 0,445. Example I. According to Example G, a catalyst is obtained from 100 g of aluminum oxide, 1 to 7.0 g of sodium hydroxide, and 3.0 g of metallic potassium. The molar ratio of A1f Oi: NaOH: K 1: 0,33: 0 ,. Example K. According to Example G, a catalyst is obtained from 100 g of alumina, 2.0 g of potassium hydroxide and 3.0 g of metallic potassium. The molar ratio of ,,: KOH: K, kk7:: 0,0542. Preparation of the catalyst from alumina, water and alkali metal. Example L. In a 200 ml capacity bottle, 100 g of j-alumina with a water content of 6.0 weight is loaded. After mixing, the alumina is heated to 200 ° C. Then, under nitrogen atmosphere / 7.6 g of metallic sodium is added. The mixture is stirred for 1 hour. After that, the temperature is raised to 400 ° C. Then 4.0 g of metallic sodium is added. The mixture is stirred for 3.5 hours and allowed to cool. Get the catalyst with a molar ratio of A1.: Nlo: Na 1: 0.3305: 0,507. Example M. In a flask with a capacity of 200 ml load 100 g of X-oxide and j-aluminum oxide with a water content of 2.0 weight. and, stirring, heated to. Then, under a nitrogen atmosphere, 5.0 g of metallic sodium is added and the mixture is stirred for 2 hours at this temperature. Get the catalyst with a molar ratio of 1: 0,115: 0,218. Example I. According to Example M, a catalyst is obtained from 100 g of X-oxide and γ-alumina with a water content of 1.6 wt.% And 3.6 g of metallic potassium, molar ratio 1: 0.092: 0.0955. Example 0. In a flask with a capacity of 200 ml load 100 g of S-alumina with a water content of 8 weight. and, stirring, heated to 300 ° C. Then, under nitrogen atmosphere, 10.5 g of sodium metal was added and the mixture was stirred for 1 hour at this temperature. Thereafter, the temperature is raised to and 4.0 g of sodium metal is added. The mixture is stirred at this temperature for 2 hours and cooled. Get the catalyst with a molar ratio of 1: 0,493: 0,695. Example P. In a flask with a capacity of 200 ml load 100 g of jr-alumina containing 10 wt.% Boehmite, A10 (OH). Heat the mixture until under an atmosphere of nitrogen, knead 3.8 g of metallic sodium. The mixture is stirred for 30 minutes at 200 ° C. Then the mixture is heated for 2 hours before and after that it is cooled. Get the catalyst with a molar ratio of A1, Oo, 1: 0,0857: 0,171. I Example 1. In a 25 ml flask, 10.0 g of ethyl-i, ms-chrysanthemate was charged, and 0.1 g of metallic sodium was added under nitrogen. Mixing while stirring is heated in an oil bath to 120 ° C. After 10, 30 and 60 minutes after the start of the reaction, samples are taken, which are analyzed by gas chromatography. The results are shown below. After complete isomerization, a small amount of ethanol is added to the reaction mixture in order to deactivate the sodium. 25 ml of cold water are then added. The mixture is subjected to extraction with 2 ml of ether 2 times. The ether extract is washed with water, dried over sodium sulfate and evaporated. The remaining liquid under reduced pressure is distilled. You move 9.1 g (915,) ethyl trons-chrysanthemum with m. Kip. 108-1 mmrt. The product is hydrolyzed in a known manner and TRNS-chrysanthemic acid with a melting point is obtained. The aqueous solution separated from the ethereal extract is acidified with 10% sulfuric acid. The oil recovered is extracted with ether. After evaporation of the ether, O. 6. g (7) of TPQHC-chrysanthemic acid is obtained. pl +9 to. Example 2. As in Example 1, 10.0 g of a mixture of 3.9 ethyl tsus-chrysanthemum and 65.1 ethyl tris-disis-chrysanthemate is heated from 0.1 g of potassium to 100 ° C. After 10, 30 and 60 minutes after the start of the reaction, samples are taken and analyzed by gas chromatography. The results are shown below. 8 mixing. After 30, 60 and 120 minutes after the start of the reaction, the robes are selected and analyzed by gas chromatography. The following results were obtained. After completion of the isomerization, the reaction mixture is treated as in Example 1. 9.1 g (91%) of ethyl trams — chrysanthemum and 0, g (7%) of ran-chrysanthemic acid are obtained. Example 4. Into a flask with a capacity of 35 ml, load 1 5, O g of oil, ms-chrysanthemum, and under nitrogen atmosphere, add 0.75 g of a 15.2% sodium dispersion in naphthalene. The mixture is heated to 120 ° C with stirring. After 10, 30, 60 and 90 minutes after the start of the reaction, samples are taken, which are analyzed by gas chromatography. The results are shown below.
    After completion of the isomerization, the reaction mixture is worked up according to Example 1. 9.2 g (92) of ethyl tPc1HC-chrysanthemate and 0.5 g (5.8%) of trans-chrysanthemic acid are obtained.
    Example 3- A 25 ml flask was charged with 10.0 g of ethyl-11, ms-chrysanthemum in a nitrogen atmosphere, 0.35 g + 0% sodium dispersion in liquid paraffin. In a water bath, the mixture is heated to
    After the isomerization is complete, a small amount of ethanol is added to the reaction mixture in order to deactivate the sodium. After adding 18 g of a 25% aqueous solution of sodium hydroxide, the mixture is heated under reflux for 2 hours and then the ethanol is distilled off. The residue is dissolved in cold water and subjected to extraction with toluene. The aqueous solution is acidified with 10% sulfuric acid and the separated oil is extracted with n-hexane. The extract is washed with water, dried and evaporated. 12.6 g of butter (98) are obtained, which is left in the refrigerator. Crystals form c. Pl. kS - 53 ° C. For purification of TPctHc-chrysanthemum acid. distilled under reduced pressure, t. bluetine acid 111-1 mm Hg. Example 5. A 200 ml flask is charged with 20 ml of anhydrous dioxane and under a nitrogen atmosphere 5.09 g of naphthalene and 0.91 g of metallic sodium. The mixture is stirred at room temperature. Sodium dissolves and forms a dark green colored complex. After 2 hours of stirring, 60.0 g of a mixture containing 35.6 ethyl-cis-chrysanthemate and 6, ethyl-trans-chrysanthemate are added. The mixture is stirred at 90 ° C. After 60, 120 and min after the start of the reaction, samples are taken and analyzed by gas chromatography. The results are shown below. After completion of the reaction, the reaction mixture is treated as in Example 4. 50.0 g {97.2%) of GRAN-brut zantemic acid with m.p. 50-53 ° C. Example 6. As in Example 4, 15.0 g of methyl cis-chrysanthemate is reacted with 0.9 g of 11% sodium dispersion in anthracene. The reaction is carried out for 3 hours with stirring. Treatment of the reaction mixture as in Example 4 gives 12.8 g of (92,) TRd-CN-chrysanthemic acid with a melting point of 9-53 ° C. Example 7. As in the example, 15.0 g of n-propyl-i, and is-chrysanthemate are carried out with 1.0 g of a 15.2% sodium dispersion in naphthalene for 6 hours with stirring and at 150 C. Reactivity the mixture is treated as in example i. 11.5 g of (95,) TRS are obtained (ns-chrysanthemic acid with the melting point of TsV-VZ C. Example 8, Into a 200 ml flask are charged 116.2 g of a mixture of 3.2 ethyl and, is-chrysanthemum and 65 , 8% ethyl trans-chrysanthemum. After displacing air from the flask with nitrogen, 2.3 g of the catalyst prepared according to Example A is added. The mixture is heated to 1–9–170 ° C with stirring. After 10, 20, 30, 60, 90 and 120 After starting the reaction, samples are taken and analyzed by gas chromatography. The results are summarized below. The reaction mixture is filtered from the catalyst and the filtrate is distilled. reduced pressure. 111.0 g (95.5) of ethyltrons-chrysanthemum are obtained with a boiling point of 108-110 ° C / 1b mm Hg Example 9. In a 25 ml flask, 8.50 g of a mixture is charged from 3.3% ethyl-iz, is-chrysanthemate and 65.7 ethyl-trans-chrysanthemate. After displacing air from the flask with nitrogen, 0.76 g of the catalyst prepared according to Example A is added. The mixture is heated to 133-137 ° C with stirring. , 60, 120 and 180 minutes after the start of the reaction, samples are taken, which are analyzed by gas chromatography. The results are shown below. The reaction mixture is filtered from the catalyst and the filtrate is distilled under reduced pressure. Get 11 8.00 g O + .l) ethyl trans-chrysanthemum with t, kip. 107-109 ° C / 1b mm Hg. Example 10. As in the example, a mixture of 36.5 pounds of ethyl and chrysanthemum and 63.5 pts of ethyl trans-chrysanthemum (6.0 g) and 1, is heated 0 g obtained according to example A of the catalyst to 59-B2 ° C. After 30, 60, 120, 180 and min after the start of the reaction, samples are taken, which are analyzed by gas chromatography. The results are shown below. Example 11. In a flask capacity of 25 ml load 5.0 ethyl-Cyo-chrysanthemum. After displacing nitrogen from the flask with air, 0.5 g of the catalyst prepared according to Example B was added. The mixture was heated to 168-173 ° C with stirring. After 20, 60 and 120 min after the start of the reaction, samples were taken. They were analyzed by gas chromatography . The results are shown below. The reaction mixture is filtered from the catalyst and the filtrate is distilled under reduced pressure. Get +, 5 g (90%) ethyl trans-chrysanthemum with so kip. 107 to 109 ° C / 17 mmHg Example 12. As in Example 9, 6.3 g of a mixture of Zb, 2 ethyl-cis-chrysanthemate and 63.8; ethyl-TPC (ns -hrizantemate with 0, g obtained according to example B catalyst up to 165-170 ° C. After 5, 30 and 90 minutes after the start of the reaction, samples are taken and analyzed by gas chromatography. The results are shown below. 7 The reaction mixture is filtered from the catalyst and the filtrate is distilled under reduced pressure. 5.6 g of 88.9 ethyl-trdns-chrysanthemate are obtained with a bp 107 ° C / 1b mm Hg. Example 13. As in example 9, 5 g of n is heated .-propyl-cis-chrysanthemate with 0.7 g of the catalyst prepared according to Example G for 2 hours to 170 ° C. Then the reaction mixture was obtained. from the catalyst and the filtrate is hydrolyzed. After neutralizing the reaction mixture, the resulting acidic part is analyzed by infrared spectroscopy. This acid part consists of a mixture of trans and chrysanthemic acids. After separation and the isomer in the form of a dihydrochrysanthemum lactone, 2.3 g are obtained (57.5%) TpdriC / -hrizantemic acid with a melting point of 8-53 ° C. Example 1. As in example 9, 5 g of α -butyl-cis-transhyrisanthemate is heated with 0.7 g of the catalyst obtained in example D within 3 hours to 170-172 ° C. Then the reaction mixture is filtered from the catalyst and the filtrate is hydrolyzed. The reaction mixture is treated as in example 1 3. 1.8 g (48) of trs1ns chrysanthemic acid are obtained. Example 15- As in Example 9, 5 g of ethyl-cis-chrysanthemate are heated with 0.6 g of the catalyst prepared in accordance with Example E for 90 minutes to 170-171 ° C. Get the reaction mixture containing 27.1 weight. ethyl-csm-chrysanthemum and 72.9 wt. ethyl-TR0ChS-chrysanthemum. Example 16. In a flask with a capacity of 25 ml load 5.0 g of ethyl-cis-chrysanthemum and 5 ml of W-heptane. After displacing air from the flask with nitrogen, 1.0 g of the catalyst prepared according to Example G was added. The mixture is heated to 60 ° C with stirring. After 1, C, 6, 7 hours after the start of the reaction, samples were taken and analyzed by gas chromatography. The results are shown below. The reaction mixture is filtered off from the catalyst and n-heptane is distilled off from the filtrate. The remaining oil is distilled under reduced pressure. Get .b g () ethyl-trance-chrysanthemum with so kip. 87 C / 5 mm Hg Example 17. A 200 ml capacity flask was charged with 11.6 g of a mixture of 32.2% ethyl cis chrysanthemum and 67.8 ethyl trans chrysanthemum. After nitrogen was displaced from the flask, 1.95 g of the catalyst prepared according to Example 3 was added. The mixture is heated to 1b9-170 ° C with stirring. After 5, 15, 30 and 60 minutes after the start of the reaction, samples are taken, which are analyzed by gas chromatography. The results are shown below. A further 0.35 g of catalyst is then added and the mixture is further stirred. After 5, 15 and 60 minutes after the catalyst supply, samples are taken, which are analyzed by gas chromatography. The results are summarized below. i The reaction mixture is filtered from the catalyst and the filtrate is distilled under reduced pressure. I get 110.7 g (9b, 6) ethyl-tpc "ns-chrysanthemum with so kip. 108-110 ° C / 1b mm Hg 18. In a 200 ml flask, 100 g of a mixture of 37.6% ethyl and ms-chrysanthemum and 62, C% ethyl-TpcjHc-chrysanthemum are loaded. After the nitrogen was displaced from the flask, 3.0 g of the catalyst obtained according to Example I was added. The mixture with stirring, heated to 130-132 ° C. After 15, B5, 120 and 270 minutes after the start of the reaction, samples are taken, which are analyzed by gas chromatography. The results are shown below. The reaction mixture is filtered from the catalyst and the filtrate is distilled under reduced pressure. Get 96 g (E () ethyl "s-chrysanthemum with a boiling point of 108-1 mm Hg. Example 19. A mixture of 2 g of I-propyl-cis - chrysanthemum and 0.8 g obtained according to For example, the catalyst is stirred for 70 minutes at 1b9-170 ° C in a nitrogen atmosphere, the reaction mixture is then processed as in Example 18, and the product is hydrolyzed in the usual manner. An acidic product is obtained, which partially crystallizes. By gas chromatography and infrared spectroscopy it was found that the acidic product consists of 23 wt. cm-chrysanthemic acid and 77 wt.% D TRans-chrysanthemum sour. After separation of the dis-isomer in the form of dihydrochrysanthemum lactone from the mixture, 1.0 g (b5%) of trans-chrysanthemic acid with a melting point is obtained. Example 20. Mixture of 4 g of n-butyl-im.-chrysantemmate and 1.2 g of the catalyst prepared according to Example K is stirred for 70 minutes at 169-170 ° C under nitrogen atmosphere, and the reaction mixture is then processed as in Example 18. The product is hydrolyzed. An acidic product is obtained, which crystallizes in part. By the method of infrared spectroscopy and gas chromatography, it was established that the acidic product consists of 29 wt. Of ChiS-chrysanthemic acid and 71 wt. Of TPctHC-chrysanthemic acid. After separation from the mixture and the is-isomer in the form of dihydrochrysanthemum lactone, 2.05 g {68.3%) trans-chrysanthemic acid is obtained. Example 21, In a flask with a capacity of 20 ml, 3.6 g of ethyl-cis-chrysantemate is charged. After the air is displaced from the flask with nitrogen, 1.2 g of the catalyst obtained according to Example L is added. The mixture is heated to 167 168C with stirring. After 5, 30, 60 and 90 minutes after the start of the reaction, samples are taken, which are analyzed by chromatography. The results are shown below. The reaction mixture is filtered from the catalyst and the filtrate is distilled under reduced pressure. Get 3, g (9,) ethyltrons-chrysanthemum with t, kip, 106-110 ° C / 17 mm Hg, st. Example 22, As in example 21, the reaction between 3 ,. g of a mixture containing 33.9 ethyl-cis-chrysanthemate and 66.1 ethyl-TRONS chrysanthemum, with 0.6 g of the catalyst prepared according to Example M at 1b8-173 ° C. 5 and 60 minutes after the start of the reaction, samples are taken which are analyzed at gas chromatography. The results are shown below. The reaction mixture is filtered from the catalyst and the filtrate is distilled under reduced pressure. Receive, 7 g (87) ethyl-tRsans-chrysanthemum with t. Kip. 107-10 ° C / 17 mm Hg Example 23. As in example 21, the reaction is carried out between k g of n-PyOg saw-and, is chrysanthemum and 0.6 g of the catalyst obtained according to example H for 2 hours at 168-172 ° C. After that, the reaction mixture is filtered from the catalyst and the filtrate is hydrolyzed. An acidic product is obtained, which is partially crystallized in Cree. Using infrared spectroscopy, it has been determined that the product is a mixture of trans-i-cis-chrysanthemic acid. After separation from the mixture of the isomer in the form of a dihydrochrysanthemum lactone, 2.2 g (68.8%) of trans-chrysanthemic acid with m, melt, 48-5 ° C, Example 24, are loaded into a 50 ml flask with 18 ml. g mixture containing 33 ethyl cis chrysanthemum and 67 ethyl trans chrysanthemum. After air is displaced with nitrogen, 3.1 g of the catalyst prepared according to Example O is added to the flask and the mixture in an oil bath is heated to 127-132 ° C and stirred. After 30, 60, 180, and 300 min after the start of the reaction, samples are taken, which are analyzed using the method of gas chromatography. The results are shown below. The reaction mixture from the catalyst is filtered off and the filtrate is distilled under reduced pressure. Get 17.1 g (93) ethyl-TRans-chrysanthemum with t, kip, 107-110 ° C / 1b mm Hg. Example 23 As in Example 21, 3 g of H-butyl u, wcxpisanthemata is reacted with 1.0 g of the catalyst obtained according to example P for 2 hours at 170-172 ° C. After that, the reaction mixture is filtered from the catalyst and the filtrate is hydrolyzed. After separation of the, and ms-chrysanthemic acid in the form of a dihydrochrysanthemum pactone from the reaction mixture, 1.6 g of (it2.7) TpdHc -chrysanthemic acid with mp. C. Example 26 A 35 ml capacity flask equipped with a reflux condenser was charged with 15.0 g of ethyl cis chrysanthemum and 0.2 g of sodium hydrite. Under nitrogen, the mixture is heated to 170 ° C. with stirring. After 10, 20, 30 and 60 minutes after the start of the reaction, samples are taken, which are analyzed by gas chromatography. The results are shown below. The reaction mixture is distilled under reduced pressure, no catalyst is isolated. Get U, 5 g (96.7%) of ethyl-tt chrysanthemum with t, kip, 87 ° C / 5 mm Hg, Art. The product is hydrolyzed. Receive trans-chrysanthemic acid with so pl. 8-53 ° C. Example 27. Repeat Example 26, but the process is carried out at different temperatures. The results are shown in Table. 1, Example 28, A 200 ml flask was charged with 100 g of a mixture containing 3.7 ethyl cis chrysanthemum and 65.3 ethyl trans chrysanthemate. After the air was displaced from the flask with nitrogen, 2.0 g 53% - dispersion of sodium hydride in mineral oil. The mixture in the oil bath is heated to 1–9–170 ° С and stirred. After 10, 20, 30. and 60 minutes after the start of the reaction, samples are taken, which are analyzed by gas chromatography. The results are shown below. I The reaction mixture with the catalyst is distilled under reduced pressure. 95.5 g are obtained (95.5 ethyl truss chrysanthemum with t, bales 108-110 ° C / 1b mm Hg, St, Example 29. Example 28 is repeated, but the reaction is carried out at different temperatures. The results are given in Table 2, Example 7, Example 28 is repeated, but different amounts of sodium hydride are used.The results are shown in Table 3. Example 31 According to Example 26, 15.0 g is isomerized with i-propyl-ukV c. -chrisite with 1.0 g of potassium hydride. Isomerization is completed in minutes, after which the catalyst is filtered and the filtrate is hydrolyzed. The acidic product is analyzed by infrared spectrometry. gas chromatography and gas chromatography. The product consists of 21% by weight of cs-chrysanthemic acid and 79 o.t.RHO-chrysanthemic acid. Example 32 According to example 26, 7.0 g of is-butyl-cis-chrysanthemate isomerized with 0.7 g of sodium hydride. After 60 minutes, the reaction mixture is analyzed by gas chromatography. It contains 25% by weight, is isomers and 75% by weight. Tris-isomers. The mixture is hydrolyzed and, ms., Chrysanthemum acid is isolated in the form of dihydrochrysanthemum lactone. 3.9 g (7.3) of trans-chrysanthemic acid are obtained .. T a b l and a, m and 1
    权利要求:
    Claims (3)
    [1]
    Claim
    1. The method of obtaining 2,2-dimethyl-3- (2 1- methyl) -1-propenyl-1,3-trcns-cyclopropane-1-carboxylic acid and its alkyl esters having in the ether part from one to four carbon atoms , by isomerizing the cis isomers of the esters of the corresponding acid in the presence of an alkaline catalyst when heated, characterized in that, in order to increase the yield of the target product, metal or molten or dispersed potassium, or sodium, or their hydroxides, or their alumina dispersed mixture at atomic or molar ratios AI ^ OjcNaOH or KOH: K or Na, equal to 1: 0.025-0.5: 0, 05 ~ 0.5; or Α1ι ^ 0 ^: Ηιχ0: Κ or Na equal to 1: 0.08-0.5: 0.09-0.7, or an alkali metal hydride in an amount of 0.00ΙΟ, 5 mol per mol of the original cis isomer, and isomerization is carried out at 50-180 ° C.
    [2]
    2. The method according to. p. 1, characterized in that the isomerization is carried out in an inert solvent.
    Priority according to signs: 16.05.72 - catalyst - metallic potassium or sodium.
    05/18/72 - the catalyst is a mixture of potassium or sodium, their hydroxide and aluminum oxide.
    [3]
    5.06.72 - catalyst - alkali metal hydrides.
    1.03.73 - catalyst - molten or dispersed potassium or sodium
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    同族专利:
    公开号 | 公开日
    DK140694B|1979-10-29|
    GB1426000A|1976-02-25|
    DK140694C|1980-05-19|
    IT986561B|1975-01-30|
    DE2324473A1|1973-11-29|
    DE2324473B2|1977-08-11|
    FR2184867B1|1977-02-18|
    NL7306857A|1973-11-20|
    CH581088A5|1976-10-29|
    CA999011A|1976-10-26|
    FR2184867A1|1973-12-28|
    US3906026A|1975-09-16|
    DE2324473C3|1978-04-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3046299A|1958-07-28|1962-07-24|Rhone Poulenc Sa|Process for the preparation of cyclopropane-carboxylic acids of transform|
    GB1005722A|1963-04-23|1965-09-29|Sumitomo Chemical Co|Process for producing trans-chrysanthemic acid esters|JPS5234618B2|1974-06-15|1977-09-05|
    FR2348901B1|1976-04-23|1983-01-28|Roussel Uclaf|
    FR2375161B1|1976-04-23|1979-04-13|Roussel Uclaf|
    DE2713538A1|1977-03-26|1978-09-28|Bayer Ag|PROCESS FOR SEPARATION OF STEREOISOMER CYCLIC CARBONIC ACIDS|
    FR2396006B1|1977-06-27|1980-04-04|Roussel Uclaf|
    EP0010875B1|1978-10-27|1983-06-22|Imperial Chemical Industries Plc|Process of separating cis and trans isomers of cyclopropane carboxylic acids|
    US4473703A|1981-03-30|1984-09-25|Sumitomo Chemical Company, Limited|Method of epimerization of alkyl chrysanthemate|
    CA1306739C|1987-02-16|1992-08-25|Gohfu Suzukamo|Solid base, process for preparing the same and use of the same in preparation of internal olefins|
    US7211539B2|2003-11-24|2007-05-01|Signa Chemistry, Llc|Silica gel compositions containing alkali metals and alkali metal alloys|
    US9598531B2|2013-02-27|2017-03-21|Materia, Inc.|Olefin metathesis catalyst compositions comprising at least two metal carbene olefin metathesis catalysts|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP4885272A|JPS5318495B2|1972-05-16|1972-05-16|
    JP4969572A|JPS5318496B2|1972-05-18|1972-05-18|
    JP5625872A|JPS5516568B2|1972-06-05|1972-06-05|
    JP2547273A|JPS5612626B2|1973-03-01|1973-03-01|
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