 Process for preparing gamma-pyrons
专利摘要:
The gamma-pyrones of formula I in which the symbols have the meaning given in Claim 1 are obtained by a simple and economic "one-pot" process by reaction of a furfuryl alcohol of formula III with at least 2 equivalents of a halogenated oxidising agent, in aqueous solution at a temperature of between -50 DEG and +50 DEG C, and then the reaction mixture is heated until hydrolysis of the intermediate formed is virtually complete. The gamma-pyrones obtained can be used as products which enhance flavour and fragrance in food and cosmetic preparations. <IMAGE> 公开号:SU1015826A3 申请号:SU782631651 申请日:1978-07-05 公开日:1983-04-30 发明作者:Мотт Бреннан Томас；Патрик Брэннегэн Даниэль；Дуглас Викс Пол；Эрнст Кухла Дональд 申请人:Пфайзер Инкорпорейтед (Фирма)； IPC主号:
专利说明:
This invention relates to an improved method for producing T-pyrons of the general formula. it is Ri-s-0- R where R is hydrogen, methyl or ethyl; R, is hydrogen or methyl. These compounds can be used as flavoring agents in food products, as well as flavor enhancers in perfumes. A known method for producing y-prons of the formula I, where R is hydrogen and R. - hydrogen, methyl or ethyl, consisting in the fact that a furily alcohol derivative of the formula R (II), where R has the above values is reacted with a halogen at a temperature of from -70 to in the presence of an alcohol of the formula ROH (where R is methyl or ethyl, or electrolysis in the presence of an alcohol of the formula: The obtained compound of the formula OE b-o-f-, where R and R have the above-mentioned values, is reacted with a strong acid anhydride with a pKa from 6 to at a temperature from ambient temperature with the formation of a compound of the formula oXoX where R and R has the above values, followed by its interaction with hydrogen peroxide in an inert organic solvent medium in the presence of alkali at a temperature from 0 to and the resulting compounds of the formula 0 (VII where R and R have the above values, are reacted with a mineral acid, Lewis acid acidic ion exchange resin or organic acid at a temperature of from 25 to 16 (f C 1. The disadvantage of this method is the multistage process. The purpose of the invention is to simplify the process and expand the range of target products. This goal is achieved in that, according to the method of producing -pyrones, a furfuryl alcohol derivative of the formula where R and R have the above meanings, is reacted with two equivalents of a halide-containing oxidant selected from the group containing chlorine or bromine, or hypochlorous or hypobromic acid, or their mixtures, in an environment of an organic solvent at a temperature of from -30 to 30 seconds and the resulting 4-halohydro pyran of the formula: -L, where R and R are as defined above, R is a hydrogen atom or C is al, kil and X is a chlorine atom or bromine a is hydrolyzed by the action of an aqueous solution of a strong acid at the boiling point of the reaction medium. The process can be carried out in a single step without isolation of the intermediate 4-halo-dihydropyran of formula III. By using two equivalents of a halogen-containing oxidant in water or in a mixture of water and an organic co-oxidant, the reaction proceeds smoothly. The release of E-pyrone is greatly simplified, since the solvent, oxidizing agent, and the by-product mineral acid are all volatile and can be removed under vacuum, which helps to obtain a high crude yield — g-pyrone directly by simple concentration. The method is carried out by dissolving the furfuryl alcohol derivative in water. or in water and co-solvent. The co-solvent may be miscible or immiscible with water and may be selected from a wide variety of races. solvents, such as alkanols or diols containing C, for example, methanol; ethers containing, for example, tetrahydrofuran or isopropyl ether; low molecular weight ketones, such as acetone; low molecular weight nitriles; low molecular weight esters and low molecular weight amides. Preferred co-solvents are alkanols containing, ti, ethers containing methanol. The temperature of the solution is maintained at a level of from -30 to preferably from -10 to. The desired furfuryl alcohol is poured into this solution while a halogen-containing oxidant is added to the reaction mixture (two equivalents). If a combination solvent with a low pitching point is used, it is removed by distillation after all the additives have been added. The reaction mixture is then heated to the boiling point of the reaction medium. The usual applicable hydrolysis temperature is 100-110 ° C. Heating is carried out until the hydrolysis of the resulting 4t-halo-dihydropropane intermediate is complete (usually 1-2 hours) and the process goes into one stage without isolation of the intermediate. The acid, necessary to catalyze this final hydrolysis, is produced locally by. terry acids from intermediates formed during the reaction. If necessary, an additional acidic halogen-containing oxidizing agent may be added from chlorine, bromine, bromine chloride, hypochlorous or bromic acid or their mixtures. Chlorine bromine can be prepared On site by adding chlorine to a solution of sodium bromide or potassium or by adding bromine to a solution of sodium chloride or potassium. Hypochlorous or haematous acid can be successfully obtained on site by adding an aqueous solution of an acid (HC1 or HBg) to a solution of the hypog: alkali metal or alkaline earth metal, for example, NaOCl, KOC1 or Ca (OC1) 2. . Preferred halogen-containing oxides are chlorine and bromine chloride, which are produced on site. When using organic acids and other proton solvents, such as acetic acid, formic acid, other organic acids and alkanols, which were not strongly dried, no additional water is produced during the reaction. However, when using aprotic solvents, water and it is added to convert the intermediate 4-halogen-b-substituted 2H-pyran-3 (bH) -one to pyrone. If a low boiling point solvent is used in carrying out the reactions, it is removed by distillation before heating the reaction mixture to 100-110 ° C to hydrolytically form the intermediate 4-halo-dihydropyrane to α-pyrone. If desired, 4-halo-dihydropyran can be obtained and isolated by halogenation at a temperature of from -20 to, preferably, from 5 to 10 ° C, in the presence of an organic base, such as tri-ethyl amide. After about 30 minutes, the reaction mixture was warmed to room temperature, filtered to remove triethylamide hydrochloride, and the solvent was removed in vacuo to give 4-halo-dihydropyran. This compound is easily hydrolyzed to 3-pyrone by heating for about 1 hour in an aqueous solution, with the addition of acid. Example. In a round-bottom three-neck flask equipped with a magnetic stirrer, a gas inlet tube, a thermometer, and an addition funnel, - 20 ml of tetrahydrofuran and 50 ml of water are added. The solution is cooled to. A solution of 1- (2-furyl) -1-ethanol in 20 ml of tetrahydrofuran is poured into an additional funnel, and all this is added dropwise to the reaction flask with stirring, while chlorine (0.30 mol) is added through a feed tube gas. The rate of addition is such that the ratio of alcohol added to chlorine is 1.3: 1.5 (approximately within 30 minutes), the temperature being kept lower at this time. The reaction mixture is heated under reflux and the tetrahydrofuran is removed by distillation. When the temperature of the reaction mixture is reached, a refrigerator is connected, and heating with a refrigerator is continued for about 2 hours. The reaction mixture is then filtered hot, cooled, the pH is adjusted to 2.2, and the reaction mixture is cooled to 5 ° C. Crystallization and filtration gave 3.43 g of crude 3-hydroxy-2-methyl-d-pyrone (maltol). The aqueous filtrate is extracted with chloroform to obtain a second portion of maltol 2.58 g. Distillation of the bound solids and recrystallization from methanol gives 5.5 g (49%) of pure white maltol, with a melting point of 159.5-160 ,. PRI me R 2. Repeat the same method as in example 1, under different conditions shown in Table. 1, with a furfuryl alcohol derivative of the formula gt / 0. Example 3 Repeat the same method as in Example 2, with comparable results, using each of the following solvents: ethanol, i-propanol, i-butanol, i-butanol, t-butanol, dioxane, ethyl ether, dimethoxyethane. 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol. PRI me R 4. In a round-bottom three-neck flask equipped with a stirrer, a gas supply tube and an addition funnel, 20 ml of tetrahydrofuran, 50 ml of water and sodium bromide (0.20 mol) are added. The solution is cooled to. A solution of 1- (2-f: reyl) -1-ethanol {0.18 mol in 20 ml of tetrahydrofuran is poured into an additional funnel and all this is added dropwise to the reaction flask with rapid stirring, while chlorine gas (0, 40 mol) is added through a gas supply tube. The alcohol addition rate is such that the yellow-orange color is maintained. The temperature is maintained below by cooling with an ice bath. After the addition of alcohol and chlorine to the reaction flask is completed, the temperature is exhausted to reflux to distill off the tetrahydrofuran. The isolation method used in Example 1 was used to isolate 12.47 g of pure maltol (yield 55%). The same results are obtained when replacing sodium bromide with TtjJM bromis:; alium. PRI, me 5. Repeat the same method as in example 4, under different conditions shown in Table. 2,. using a furfuryl alcohol derivative of the formula O-C Exampleb. In a round-bottom three-neck flask equipped with a magnetic stirrer, a tube for supplying gas, a thermometer, and an additional booster, 50 ml of tetrahydrofuran AND 50 ml of water are added. This solution is then cooled to, and chlorine / 0.10 mol) is slowly added to the reaction flask, 1- (2-furyl) -1-ethanol (0.09 mol) is added dropwise. The temperature of the reaction mixture is raised to above 10c. . Bro is then added and the reaction mixture is heated under reflux. 5.7 maltol is measured using the isolation method used in Example 1 Example. In a round-bottomed four-necked flask equipped with a thermometer, a cooler and two additional funnels, 50 ml of tetrahydrofuran and 50 ml of water are placed and the solution is cooled to. Bromine (0/20 mol) and 1- (2-furyl 1-ethanol (0.09 mol) are added together to two additional funnels in this well-mixed solution. The temperature of the mixture is maintained equal to those of the total double addition. Then the reaction mixture is heated to within 10 hours. Maltol was isolated by the method described in Example 1 (53% yield). Example The method used in Example 1 is repeated under the various conditions shown in Table 1. 3, using a furfuripe alcohol derivative of the formula ExampleE. A 2.8m solution of sodium hypochlorite is prepared by passing chlorine (42.6 g) into a solution of 48 g of sodium hydroxide in 150 ml of water at. In a three-necked flask, a solution is prepared from 1- (2-furyl) -1-ethanol (0.05 mol) in 15 ml of tetrahydrofuran and 15 ml of water, and this solution is cooled to 5 times each. WITH. While maintaining the pH from 1.0 to 0.8 with the help of bn. HC, to the reaction flask, for about 33 minutes, 31.7 ml of hypochlorite solution is added dropwise, and the temperature is kept below 5 ° C. Then 15 ml of concentrated hydrochloric acid is added to the reaction mixture, and this mixture is then heated to remove the tetrahydrofuran by distillation. Heating is continued for 1 hour. Maltol is isolated in the same manner as described in Example 1. The same results are obtained using sodium hypobromate instead of sodium hypochlorite. Example 10 To a solution consisting of 1- (2-furyl) -1-ethanol (0.05 mol) in 15 ml of water, 21.7 ml of 2.8 M sodium hypochlorite is added at 5 ° C. Chlorine (0.05 mol) is added through the gas supply tube to the reaction flask and the temperature is kept below 5 ° C. The reaction mixture is then heated to reflux and the tetrahydrofuran is removed by distillation. Heating is continued for 1 hour. The reaction mixture is cooled and maltol is isolated by the method described in Example 1, Example 11. In a round-bottom three-neck flask, a solution of 50 ml of water and 20 ml of tetrahydrofuran is placed and this solution is cooled to. . A solution consisting of 1- (2-furyl) -1-ethanol and (0.89 mol) in 25 ml of tetrahydro- is placed in an additional funnel. furan, and this solution is added dropwise to the reaction chamber while adding BrCl (0.30 mol) through the gas supply tube. The rate of addition is such that all furfuryl alcohol is added at a ratio of 1.3: 1.5 equivalents of BrCl, while the temperature is kept lower at this time. The reaction mixture is heated to mode and the tetrahydrofuran is removed by distillation. When the temperature reaches, connect the refrigerator and the reaction mixture is heated under reflux for about 2 hours. The reaction mixture is cooled and maltol is isolated by the method described in Example 1. Note 12. In a round-bottom three-neck flask equipped with a magnetic stirrer, a thermometer and two additional funnels, stir 25 ml of tetrahydrofuran and 50 ml of water. To this solution add 1- (2-furyl 1-ethanol (0.89 mol) in 2S ml of tetrahydrofuran while adding drop by drop bromine (0.16 mol), and the temperature at this time is kept below 15 C. After the addition is complete, chlorine (0.10 mol) is added through a gas supply tube and the reaction mixture is heated to reflux. Mal tol is isolated from the cooled solution by the method described in Example 1. Example 13 6-Oxy-2-methyl2H-pyran-3 (6H) -one. To a solution consisting of 25 g of 1- {furyl) -1-ethanol in 125 ml of tetrahydrofuran and 125 ml of water, 1 equivalent of bromine is added. During the whole addition, the temperature is kept at 5-10 ° C. The pH of the solution was adjusted to 2.1 and the solution was extracted with ethyl acetate (3 x 50 ml). The ethyl acetate extract is dried and evaporated, which gives a yellow oil. This oil is chromatographed on silica gel and eluted with chloroform-egylacetate (3: 1) to give 4.8 g of light oil, which, as shown by spectral analysis data, is identical to 6-hydroxy-2-methyl-2H-pyran-3 (bN) -one obtained from 6-methoxy-2-methyl-2H-pyran3 (bH) -one by acid hydrolysis. Infrared spectroscopy (СНС1 0700, 3300, 1700 cm-. Nuclear magnetic resonance (CDCl: 6.8-7.1 (1H d from d); 6.0-6.2 (GN, d), 5.6 (1H, Lg, S, exchanges with DaO); 5, 4-5.5 (IH, d. ); 4, 8-5, 5 (lH, q 1.3-1.6 (ЗН, t). Example 1 four. The method described in Example 13 is repeated to obtain the compound of the formula h. O and get 6-hydroxy-2-ethyl-311-pyran | 3 (6H) -one. Infrared spectroscopy (SNSC 3600, 3340, 1706 6 - OXI-3N-PI ran-3 (6H) -one. Infrared spectroscopy (СНС 3565, 3300, 1703 СМ-. Example 15 4-Bromo-6-hydroxy-2methyl-2H-pyran-3 (6H) -one. To a solution consisting of 25 g of 1- (2-furyl) -1-ethanol in 125 ml of tetrahydrofuran and 125 ml of water, 2.2 equivalents of bromine are added dropwise. During the whole addition the temperature is maintained at the level of 5-10 C. After the addition of bromine, the solution is stirred at room temperature for 20 minutes, and the pH is adjusted to 2.1 with 2N NaOH solution. The reaction mixture was extracted with ethyl acetate (3x100 ml). The ethyl acetate extracts are mixed, dried on MgSQ, filtered and dried. The residue is chromatographed on silica gel and eluted with chloroform-ethyl acetate (95: 5). The product obtained is orange oil, which is subjected to a repeated chromatographic analysis on silica gel and eluted with chloroform-ethyl acetate (95: 5). Nuclear magnetic (CDCl) 7.3 (1H, d); . 5.6 (1H, d); 4.7-5.0 (lH, q); 1.1-1.5 (3N, m). PRI me R 16. The method used in Example 15 is repeated and the 4-bromo-6-hydroxy-2-ethyl-2H-pyran-3 (bH) -one is obtained. Nuclear Magnetic Resonance (CDClo), 7.4 (lH, d); 4.6-4.9 (lH, m); 1.3-2.2 (2H, m); 1.0-1.3 (3H, t). 4-Bromo-6-hydroxy-2H-pyran-3 (6H) -one. Nuclear magnetic resonance (SOSTS, cG) 7.4 (lH, d); 5.5 (1H, a); 4.6 (2H, d from d). Example 17 A solution of 4-bromo-6-hydroxy-2-methyl-2H-pyran-3 (bN) -one is prepared by dissolving this compound in an aqueous inorganic solution or in an aqueous solution of an organic acid. The solution is then heated under reflux, cooled to room temperature, the pH is adjusted to 2.1 with NaOH and the reaction mixture is extracted with chloroform. Concentration gives maltol. Acids, reaction time and yields for maltol are given in table. four. . Organic solvents such as benzene and toluene can be used along with acidic materials such as steam. a-toluenesulfonic acid and. Amberlite. IN-120. Example 18 The method described in Example 15 was repeated using chlorine instead of bromine and the corresponding furfuryl alcohols to give the following compounds: 4-Chloro-6-hydroxy-2-methyl-2H-pyran-3 (bN) -one. Nuclear magnetic resonance (CDC1,, сГ) 7.1 (lH, d); 5.8 (lH, d); 4.6-5.0 (lH, m); 4.4 (lH, br, S). ; 1.2-1.5 (3H, m); 4-Chloro-b-hydroxy-2-ethyl-2H-pyrac-3 (bH) -one. Nuclear magnetic resonance {CDC1,, (f) 7.0-7.1 (lH, d); 5.6-6.0 (2H, m); 4.4-5.0 (lH, m); 1.6-2.3 (2H, m); 0.9-1.1 (3H, t); 4-Chloro-6-hydroxy-2H-pyran-3 {6H) -one Nuclear magnetic resonance (CDCl, cf) 7, l-7.2 (lH, d); 5.6 (lH, d) 4.4-4.9 (2H, d from d) (Example 19, 6-methoxy-2-methyl-2H-pyran-3 (6H) -one solution was added (0.01 mol) in 20 ml of acetic acid is treated with chlorine gas (0.01 mol) at room temperature. The reaction mixture is then heated under reflux for approximately 1 hour, cooled to room temperature, diluted with 20 ml of water, the pH is adjusted to 7.0 with 50% NaOH solution, and then the reaction mixture is extracted with chloroform. The chloroform extract is concentrated to obtain maltol, which is recrystallized from methanol to yield pure product (56%), having a melting point of 159-160 ,. Ex. 20. The method described in Example 19 was repeated, with comparable results being obtained by replacing acetic acid with each of the following solvents: formic acid, methanol, ethanol, tetrahydrofuran, benzene, ethylene glycol, trifluoroacetic acid, acetone, acetonitrile. Example 21 The method described in Example 19 is repeated, with comparable results obtained and replacing chromium with bromine, hypochlorite or hypobromite with potassium or sodium, gaseous bromine chloride or chlorogram of bromine obtained on-site by adding chlorine to the solution containing sodium bromide or bromine solution sodium chloride. PRI me R 22. 4-Chloro-6-methoxy 2-methyl-2H-pyran-3 (bN-) -one. To a solution of 6-methoxy-2-methyl-2N-pyran-3 (6H) -one (0.05 mol) in 70 ml of dichloromethane at -10 ° C is added chlorine (0.05 mol) through a gas supply tube. After this addition, triethylamine (0.05 mol) is slowly added, at which time the temperature is kept equal. After 30 minutes of stirring, the mixture is allowed to warm to room temperature, then it is filtered to remove triethylamine hydrochloride and the solvent is removed under vacuum. Re-dissolving the crude product in benzene ether and filtering removed the last traces of triethylamine hydrochloride. Removal of the solvent gives 4-chloro-6-methoxy-2-methyl-2H-pyran-3 (6H) -one (yield 99%). Nuclear magnetic resonance analysis of signals at 5.05-5.25 clearly shows two doublets in a ratio of 1: 3, which corresponds to the proton at C-6 of two possible compound isomers. Example 23 4-Bromo-6-methoxy2-methyl-2H-pyran-3 (6H) -one. The method described in Example 22 was repeated, replacing chlorine with bromine and obtaining 4-bromo-6-methoxy-2H-pyran-3 (6H) -one with a yield of 93%. PRI me R 24. 4-Bromo-6-acetyl2H-pyran-3 (6H) -one. A 6-acetoyl2H-lyran-3 (6H) -one solution in dichloromethane is brominated in the manner described in Example 6 to afford 4-bromo-6-acetyl-2H-pyran-3 (bN) -one having a melting point of 78-80 WITH. The mass spectrum of the compound shows the expected maxima at 234 and 236 mass units. Example 25 4-Bromo-6-acetyl-2-methyl-2H-pyran-3 (6H) -one. The method described in Example 24 was repeated using 6-acetyl2-me, thyl-2H-pyran-3 (6H) -one and to give 4-bromo-6-acetyl-2-methyl2H-pyran-3 (6H) -one, which shows a maximum of 249.96 and 247.96 during mass spectroscopy and the following nuclear magnetic resonance spectrum: (cG,. SOS1d): 7.3 (lH, d); 6.4 (lH, doT-d); 4.7 (lH, q); 2.2 (3H, S) 1.4 (3H, S). P p and M e p 26. 4-chloro-6-methoxy-2-methyl-2H-pyran-3 (6H) -one and acetic acid are added to a round bottom flask equipped with a stirrer and a condenser and the reaction mixture is heated under reflux for 1 hour. When cooled, maltol is obtained (65%). PRI me R 27. The method described in Example 26 is repeated to give comparable results using formic acid instead of acetic acid. PRI me R 28. 6-Methyl-2-ethyl-3oxy-4H-pyran-4-one. 38 are placed in a round bottom three-neck flask. ml of methanol and 38. ml of water. The solution is cooled to and 0.166 mol of 5-methyl-2- (2-hydroxypropyl) and 0.416 mol of chlorine are added at the same time. During the addition, the temperature is maintained in the range of from -16 to -8 ° C. After the addition is complete, the solution is heated to 80 ° C and refluxed for approximately 3 hours. After cooling to room temperature, the pH was adjusted to 2.1 and the mixture was extracted with chloroform (3x100 ml). The combined organic layers were washed with water, turned into brine and dried over magnesium sulfate. The organic solution is filtered and evaporated, which gives a dense dark solid. The solid is recrystallized twice from methanol, giving 8.06 g (yield 30%) of a white solid. Sublimation gives a pure product having an isv-isg c point. Calculated from C 62.33; H 6.54 CBH, OOE Found: C 62.05; H 6.44 Nuclear magnetic resonance (CDCl,, (f); 6-CH, 2.33 (3H, S); 2-CH}, 1.30 (3H, t); 2-CH2-, 2, 75 (2H, quartet), 5H, 6.33 (1H, S). Example 29 2,6-Dimethyl-Zoxyg 4H-pyran-4-one. 28 ml of water and 32 ml of methanol are added to the round-bottom three-neck flask and the mixture is cooled to -15 ° C. Rust thief is treated with 0.167 mo of 5-methyl-2- (o-oxyethyl) furan and 0.416 mol of chlorine simultaneously. The temperature is kept between -15 and -10 ° C during the addition. The mixture is allowed to warm to room temperature over 30 minutes and then it is heated under reflux for 3 hours. The pH of the cooled solution was adjusted to 2.1. The one-step method using an oxidant and the solution extracted with chloroform (3x100 ml). The chloroform extracts are mixed, washed with water and converted into brine, dried over magnesium sulfate, filtered and evaporated. The residue is a dark oil is subjected to chromatographic analysis on silica gel using methylene chloride. and ethyl acetate (95: 5). The product recovered by evaporation is recrystallized from methanol as a tan solid (25% yield). Sublimation gives white crystals having a melting point of 161-1 ° C. Calculated: G 59.99; H 5.75 Found: C 59.83; H 5.82 Nuclear magnetic resonance (CDC1, ..., cf); 6-CH, 2.33 C3H, S); 2-CH3, 2.26 (3H, S); 5-H, 6.10 (1H, S). . The advantage of the proposed method is that it allows the process to be carried out in one stage, as well as to obtain a whole series of d-pyrones. the quality of Ta blitsa 1 -thirty SI, THF is tetrahydrofuran; This SLA is ethyl acetate. 50 110 one-step process using chlorine 32 32 18 25 18 35 35 Table3 Table4 68 52 35 49 24 26 29 5 5 3 5 2 2 Table2 as BrCl oxidant, in place in NaBr : i: n 35 H He is diluted 35 H He is diluted by H 1 I 35 101582616 Continued table. four : j:; ::::: i ::::: i :::: I 269 336 30.4 370 377 3 24 five 48
权利要求:
Claims (1) [1] METHOD FOR PRODUCING ^ —PYRONOSIS of the general formula 0 * have the indicated meanings where R is hydrogen, methyl or ethyl; R ^ is hydrogen or methyl, based on a derivative of furfuryl alcohol using acid hydrolysis, characterized in that, in order to simplify the process and expand the range of target products, a derivative of furfuryl alcohol of the general formula NII; ; R r is hydrogen or Cf_4 alkyl; X - chlorine or bromine, is subjected to hydrolysis by the action of an aqueous solution of a strong acid at the boiling point of the reaction medium. Priority by signs: 08/02/76 at HC - hydrogen; R is hydrogen, methyl or ethyl; 09.09.76 with HC - methyl; R is hydrogen, methyl or ethyl. G: l eo S3
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公开号 | 公开日 PT66694A|1977-07-01| NO821851L|1978-02-03| PL115497B1|1981-04-30| IE45644B1|1982-10-20| SE8200519L|1982-01-29| HU185687B|1985-03-28| JPS5318578A|1978-02-20| NL170955B|1982-08-16| JPS5618596B2|1981-04-30| SE444565B|1986-04-21| NL182477B|1987-10-16| NL170955C|1983-01-17| GB1538372A|1979-01-17| IE45645B1|1982-10-20| FI72720B|1987-03-31| IE45643B1|1982-10-20| PH13926A|1980-11-04| NO834236L|1978-02-03| AR216080A1|1979-11-30| AT363470B|1981-08-10| HK30381A|1981-07-10| ES459994A1|1978-11-16| JPS5436267A|1979-03-16| DK153483B|1988-07-18| IE790586L|1978-02-02| IT1106258B|1985-11-11| MX4597E|1982-06-25| FI831703L|1983-05-16| FI72720C|1987-07-10| NL182805B|1987-12-16| MY8100262A|1981-12-31| HK30781A|1981-07-10| DK276177A|1978-02-03| NO150560C|1984-11-07| NO150043B|1984-04-30| DK326086D0|1986-07-09| MY8100267A|1981-12-31| NL182805C|1988-05-16| GR68938B|1982-03-29| PL199798A1|1979-08-27| IE45641B1|1982-10-20| NL7706811A|1978-02-06| NO821850L|1978-02-03| DK153484B|1988-07-18| GB1538375A|1979-01-17| NZ184342A|1978-09-25| SE444564B|1986-04-21| ATA124480A|1981-01-15| MY8100287A|1981-12-31| DK153401B|1988-07-11| DK153483C|1988-11-28| NO821847L|1978-02-03| FI831700L|1983-05-16| NO821849L|1978-02-03| GB1538373A|1979-01-17| LU77600A1|1978-02-01| PL115586B1|1981-04-30| ES470743A1|1979-01-16| CS203921B2|1981-03-31| DK326186D0|1986-07-09| DE2728499C2|1986-04-03| JPS5729034B2|1982-06-19| PL215006A1|1979-12-17| CH625235A5|1981-09-15| TR19652A|1979-09-17| FI831702L|1983-05-16| IE790584L|1978-02-02| NL8105538A|1982-04-01| CH626358A5|1981-11-13| SE8200522L|1982-01-29| FI72119B|1986-12-31| DE2760220C2|1987-08-20| FI831700A0|1983-05-16| FR2372821B1|1980-10-17| NO772193L|1978-02-03| CA1117541A|1982-02-02| IE45642B1|1982-10-20| BG28849A3|1980-07-15| ATA440477A|1980-11-15| DK326086A|1986-07-09| GB1538371A|1979-01-17| NO150042C|1984-08-15| NO150561C|1984-11-07| BG28988A4|1980-08-15| CH626357A5|1981-11-13| SE8200520L|1982-01-29| NL182477C|1988-03-16| NO151365C|1985-03-27| RO78953A|1982-04-12| NO151365B|1984-12-17| NL182476B|1987-10-16| CA1095921A|1981-02-17| NO150561B|1984-07-30| FI72119C|1987-04-13| PL215008A1|1979-12-17| HK30481A|1981-07-10| ES470746A1|1979-01-16| NL8105540A|1982-04-01| AT364356B|1981-10-12| FR2372821A1|1978-06-30| ATA124380A|1981-03-15| DK153401C|1988-11-28| DK326186A|1986-07-09| PH13557A|1980-06-26| YU43190B|1989-04-30| YU166383A|1986-02-28| FI72723C|1987-07-10| YU42613B|1988-10-31| FI72723B|1987-03-31| HU180040B|1983-01-28| CS203923B2|1981-03-31| YU40166B|1985-08-31| DK154079B|1988-10-10| NO150559C|1984-11-07| DE2728499A1|1978-02-09| CA1110254A|1981-10-06| SE433079B|1984-05-07| PH14625A|1981-10-12| FI831702A0|1983-05-16| NO150560B|1984-07-30| JPS5436270A|1979-03-16| IE790585L|1978-02-02| FI72722B|1987-03-31| JPS5618597B2|1981-04-30| CH625798A5|1981-10-15| JPS5420500B2|1979-07-23| BG28989A4|1980-08-15| SE445041B|1986-05-26| HU186026B|1985-05-28| DK153484C|1988-11-28| PL115496B1|1981-04-30| FI831701A0|1983-05-16| PT66694B|1978-11-17| SE445042B|1986-05-26| BE855965A|1977-12-21| NL182476C|1988-03-16| NO150042B|1984-04-30| FI831704L|1983-05-16| JPS5436266A|1979-03-16| ES470744A1|1979-01-16| RO74367A|1981-11-24| PL215007A1|1979-12-17| PH13874A|1980-10-24| JPS5436268A|1979-03-16| FI771934A|1978-02-03| DE2760221C2|1989-10-05| NL182478C|1988-03-16| BG29136A3|1980-09-15| GB1538374A|1979-01-17| HU185686B|1985-03-28| YU274782A|1983-12-31| AU2601777A|1978-09-21| HK30581A|1981-07-10| SE7707035L|1978-02-03| JPS5814433B2|1983-03-18| EG13080A|1981-03-31| YU146977A|1983-06-30| FI72721B|1987-03-31| NL182478B|1987-10-16| DD132494A5|1978-10-04| DK325986D0|1986-07-09| YU270382A|1983-10-31| JPS5436269A|1979-03-16| SE8200518L|1982-01-29| CS203922B2|1981-03-31| NO150559B|1984-07-30| NO821848L|1978-02-03| FI73424C|1987-10-09| IE790587L|1978-02-02| ES470745A1|1979-01-16| IE45641L|1978-02-02| FI831704A0|1983-05-16| RO78952A|1982-04-12| SU955859A3|1982-08-30| SE452616B|1987-12-07| BR7703970A|1978-07-04| DK325986A|1986-07-09| DK154079C|1989-02-27| NL8105537A|1982-04-01| FI831703A0|1983-05-16| NO150043C|1984-08-15| NL8105539A|1982-04-01| FI72721C|1987-07-10| PH15185A|1982-09-10| FI73424B|1987-06-30| FI72722C|1987-07-10| AT362790B|1981-06-10| SE8200521L|1982-01-29| FI831701L|1983-05-16| JPS5436271A|1979-03-16| RO78951A2|1982-04-12| HK30681A|1981-07-10|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 US3491122A|1966-09-14|1970-01-20|Monsanto Co|Synthesis of 4-pyrones| US3547912A|1968-07-29|1970-12-15|American Home Prod|Derivatives of 2h-pyran-3-ones and preparation thereof| JPS5145565B1|1968-10-12|1976-12-04| US3621063A|1968-12-24|1971-11-16|Monsanto Co|Unsaturated acyclic ketones| US3832357A|1971-05-26|1974-08-27|Daicel Ltd|Process for preparation of 3-hydroxy-2-alkyl-4-pyrone| JPS5412465B2|1975-07-17|1979-05-23| IE42789B1|1975-08-28|1980-10-22|Pfizer|Preparation of gamma-pyrones| CA1095921A|1976-08-02|1981-02-17|Thomas M. Brennan|Preparation of gamma-pyrones|CA1095921A|1976-08-02|1981-02-17|Thomas M. Brennan|Preparation of gamma-pyrones| JPS5444675A|1977-09-12|1979-04-09|Shin Etsu Chem Co Ltd|Production of 3-hydroxy-4-pyrone analog| FR2402654A1|1977-09-12|1979-04-06|Shinetsu Chemical Co|Tetra:hydro-pyranone derivs. - useful as intermediates for cpds. used as food flavours| JPS5741226U|1980-08-20|1982-03-05| JPS59135008U|1983-02-28|1984-09-10| JPS6050245A|1983-08-29|1985-03-19|Nissan Motor Co Ltd|Fuel injection device in internal-combustion engine| JPH0226945Y2|1985-09-11|1990-07-20| JP2586607B2|1987-10-30|1997-03-05|日産化学工業株式会社|Production method of optically active alcohol| WO2008116301A1|2007-03-28|2008-10-02|Apotex Technologies Inc.|Fluorinated derivatives of deferiprone| EP2268282B1|2008-04-25|2014-10-29|Apotex Technologies Inc.|Liquid formulation for deferiprone with palatable taste| RS53642B1|2009-07-03|2015-04-30|Apotex Technologies Inc.|Fluorinated derivatives of 3-hydroxypyridin-4-ones| WO2017168309A1|2016-03-29|2017-10-05|Dr. Reddy’S Laboratories Limited|Process for preparation of eribulin and intermediates thereof| CN108609456B|2016-12-13|2021-03-12|奥的斯电梯公司|Openable expansion panel and elevator suspended ceiling, elevator car and elevator system with same|
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申请号 | 申请日 | 专利标题 US71090176A| true| 1976-08-02|1976-08-02| US05/721,885|US4082717A|1976-08-02|1976-09-09|Preparation of gamma-pyrones| 相关专利
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