• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    C11-C12 branched aliphatic unsaturated ketones are described, as well as a process of organoleptically modifying augmenting or enhancing therewith and a process for producing a staple single phase aqueous alkaline metal hypochlorite solution containing the same.
    公开号:SU1194268A3
    申请号:SU813298900
    申请日:1981-06-18
    公开日:1985-11-23
    发明作者:М.Боден Ричард；Деккер Ламберт；Луис Шмитт Фредерик；Г.Ван Ловерен Аугустинус；Х.Гейгер Младший Джон
    申请人:Интернэшнл Флейворз Энд Фрейгранс Инк (Фирма)；
    IPC主号:
    专利说明:

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    Yu
    about
    00 1 The invention relates to organic chemistry, in particular, to a process for the preparation of new derivatives of diisoamylene of the general formula O, where one of the dotted lines indicates a carbon-carbon double bond, each of the remaining dotted lines means a simple carbon-carbon bond, and R — C — C - lower alkyl, which may find use in perfume compositions as fragrant and aromatic substances. The aim of the invention is to find a way to obtain new scented and aromatic substances. Example 1. Getting diisoamine. 2-Methyl-2-butene is pumped for 10 hours through a 5x0.625 inch (127 X 16 mm) tube filled with 15 g of catalyst — polystyrene sulfonic acid, at 100 ° С and a pressure of 28.1 atm. . The resulting product is distilled on a fractionation column in order to separate the diisoamylene from the higher polymer polymer molecules that are formed as by-products during the reaction. Example 2 Preparation of acetyl derivative of diisoamylene In a two-liter reaction flask equipped with a stirrer, thermometer, reflux condenser and jacket, 100 g of acetic anhydride and 80 g of boron trifluoride ether are placed. To the mixture was added 690 g of diisoamylene prepared analogously to example 1. The reaction mixture was held at 8285 ° C for 5.5 hours, after which it was cooled to room temperature. Then the reaction mass is added to 1 liter of water and the resulting mixture is stirred, resulting in the formation of an organic and aqueous phase. The organic phase is separated from the aqueous phase and neutralized with two liters of a 12.5% sodium hydroxide solution, then washed with 1 l of a saturated sodium chloride solution. The resulting organic phase is then dried over anhydrous sodium sulphate and distilled on a column with a 1.1DAY plate, to obtain the fractions shown in table. 1. The resulting material is then distilled on a multi-plate rectifi- cation. the column, having obtained fractions at reflux numbers (reflux / distillate); 2. The resulting product was characterized by GOCH, NMR, IR and mass spectrometry as a mixture of cis and trans isomers of compounds of the general formula, where. Example 3: Preparation of the propionyl diisomylene derivative. In a five liter reaction flask: equipped with a reflux condenser, a dropping funnel, a thermometer, a thermostat, a heating jacket and a device for purging with nitrogen, 1000 g (7.45 mol) of propionic anhydride and 91.4 ml (0.745 mol) of boron trifluoride etherate are placed. The resulting mixture was heated to 65 ° C. 1501 ml (7.45 mol) of diisoamylene, prepared in the same way as in Example 1, was added over 25 minutes, maintaining the temperature of the reaction mass at 65-70 ° C. Then, the reaction mass was mixed in. for 30 minutes at 65 ° C, after which it is cooled down into a three-liter separating funnel. Then 75 ml of water are added with the following 75 ml of 50% sodium hydroxide solution and 25 ml of water, the reaction mass is drawn into a beaker and cooled to room temperature using a bath — dry ice in isoproyl alcohol. Thereafter, the reaction mass is added to a five-liter separatory funnel, and the lower aqueous layer is removed. The upper organic phase is washed with 500 ml of saturated sodium chloride solution. Then, the organic phase is washed with 500 ml of 5% sodium hydroxide solution, 500 ml of saturated sodium chloride solution and 500 ml of 5% sodium hydroxide solution until the pH of the oil is in the range of 6-7. The oil is then washed again with 500 ml of a complete solution of sodium chloride. The aqueous phase is extracted with 400 ml of diethyl ether. The resulting material is then distilled on a 50.8 mm spray column and the fractions shown in Table 2 are obtained. 3. 3 Fractions 5-7 are combined for re-distillation on a 25, A mm column, and the fractions shown in Table 2 are obtained. 4. Using GLC, NMR, IR and mass spectrometry, the resulting product was characterized as a mixture of a compound of the general formula, where. Example 4. Preparation of n-butyryl diisoamylene derivative. In a five liter reaction flask equipped with an electrical stirrer. 960 g of n-butyric anhydride and 105 ml of boron trifluoride are added with a heating jacket, a thermometer, a dropping funnel and a reflux condenser. The reaction mixture is heated to 65 ° C and 1725 ml of diisoamylene, prepared in the same manner as in Example 1, is added dropwise over the course of 3.5 hours, while the temperature of the reaction mixture is maintained at. At the end of the addition, the reaction mixture is cooled to 38 ° C and then transferred to a 5 L separatory funnel. Then, 75 ml of a 50% aqueous solution of sodium hydroxide and 100 ml of water are added to the reaction mass. The organic phase is washed with 1 liter of saturated sodium chloride solution until the pH is 4-5. The reaction mixture is then washed with 1 l of a 12.5% solution of sodium hydroxide, stirred for 15 minutes and separated. Thereafter, the obtained organic phase is dried over anhydrous magnesium sulphate, distilled on a 25.4 mm Stone column, and the fractions shown in Table 2 are obtained. 5. The obtained fractions 7–9 are combined and distilled again for a 616 mm high stainless steel count. The fractions shown in Table 2 are obtained. 6., Using GLC and IR spectrometry, the resulting product is characterized as a mixture of compounds of the general formula, where. Example 5. Preparation of isobutyral derivative of diisoamylene. In the reaction flask with a capacity of 5 l equipped with a reflux condenser, a dropping funnel, a thermometer, a thermostat, a heating jacket, and a device for flushing with 8 nitrogen, 1361 g (8.6 mol) of isobutyryl anhydride are placed. Then 105 ml (0.86 mol) of boron trifluoride etherate are added to the isobutyric anhydride. The resulting mixture is then heated to. 1725 g (8.6 mol) of diisoamylene, prepared as in example 1, are added to the reaction mixture for 4 hours, while the temperature of the reaction mixture is maintained at 83-85 ° C. The reaction mixture is then cooled to room temperature and poured into 5 liters separating funnel. Then, 75 ml of a 50% aqueous solution of sodium hydroxide and 100 ml of water are added to the reaction mixture. The lower aqueous phase is removed, and the organic phase is washed with 1 L of saturated sodium chloride solution, 1 L of 5% sodium hydroxide solution, 1 L of sodium chloride, 1 L of 12.5% sodium hydroxide solution, 1 L, 12.5% sodium hydroxide solution. The reaction mixture is then distilled on a spray column (50.8 mm) filled with stone fines, and the fractions shown in Table 2 are obtained. 7. Fractions 5 and 6 of the distillate obtained after distillation are combined and re-distilled, and the fractions shown in Table 8 are obtained. Fractions 3–9 of this distillate are then combined, distilled again and the fractions shown in Table 1 are obtained. . 9. Using the GLC, NMR, IR and mass spectrometry methods, the resulting product was characterized as a mixture of compounds summarizing the formulas, where K iso-C P y. Example 6. Preparation of acetyl derivative of diisoamylene. Into a 5 L reaction flask equipped with an electric stirrer, a thermometer, a dropping funnel, a 24/42 U-tube, a refrigerator, a heating jacket and a nitrogen purge device, add 41 ml of 70% methanesulfonic acid and 30 g of phosphorus pentoxide. The resulting mixture is exothermically heated to 60 ° C. Over 7 minutes, 235 ml of acetic anhydride was added to the reaction mixture, maintaining the temperature at 65 ° C. Maintaining the reaction temperature of the 5 Research Institute at 80 ° C, 516 kp of diisoamylene, obtained in a manner similar to Example 1, was added dropwise to the reaction mass. At the end of the addition of diisoamylene, according to GLC, the reaction mixture contained 42% of the product. The reaction mixture is poured into a separating funnel with a capacity of 15.1 liters with the lid open, which contains 1 liter of water. The resulting mixture was washed with 1 L of a 12% aqueous solution of sodium hydroxide and then 1 L of a saturated solution of sodium chloride. To facilitate separation, 100 ml of toluene are added. According to GLC, NMR, IR and mass spectrometry, the resulting product was characterized as a mixture of compounds of the general formula 1, where. The resulting reaction product is then dried over anhydrous magnesium sulphate and distilled on a column with stone fines of 76 mm in size to obtain the fractions presented in table. 10. Example 7. Preparation of acetyl derivative diiaoamylene. In a 500 mm reaction flask equipped with a reflux condenser dropping funnel, a thermometer, a thermostat, a heating jacket, a cooling bath and a device for purging with nitrogen, 406 ml of acetic anhydride and 30 ml of boron trifluoride etherate are added. The reaction mixture is heated to 60 ° C, and maintaining the temperature of the reaction mass at 60 ° C, diisoamylene prepared in the same manner as in Example 1 is added over 30 minutes. Then, the resulting reaction mixture is heated at 60 ° C and stirred for 12 hours. At the end of this period and the reaction mixture is distilled and the fractions shown in Table 11 are obtained. According to the data of HEC, LC and NMR spectroscopy and mass spectroscopy, the resulting product was characterized as a mixture of compounds of the general formula, where R is CHj. Example 8. Preparation of a propionyl diioamoilV derivative of a 5 l reaction flask equipped with a reflux condenser, a dropping funnel, a thermometer, a thermostat, a heating bath, a cooling bath, and a nitrogen purge device, was added 415 ml of propionic anhydride, 11 g of methanesulfonic acid boron trifluoride etherate. The reaction mass is heated to 60 ° C and 1850 ml of diisoamylene prepared as in Example 1 are added over 30 minutes. The reaction mixture is then stirred for 12 hours at 60 ° C, after which it is distilled on a fractionation column to obtain a mixture of compounds of the general formula, where. Example 9. The preparation of isobutyryl diisoamylene. Into a 5 l reaction flask equipped with a reflux condenser, a dropping funnel, a thermometer, a temperature controller, a heating jacket, a cooling bath, and a nitrogen purge device, add 953 ml (6.0 mol) of isobutyryl anhydride, 183 g of polyphosphoric acid and 135 ml 70 % methanesulfonic acid. This reaction mixture is heated exothermically to. Within 20 minutes, maintaining the temperature of the reaction mixture at, 1725 g (8.6 mol) of diaoamylene prepared in the same way as in Example 1 are added. Then the reaction mixture is heated to 85 ° C and held at it for 10 hours, after which it is cooled and 100 g of sodium acetate and 1 l of water are added to it. The resulting mixture is added to a separating funnel with a capacity of 5 liters and the organic layer is then washed with 1 L of 12.5% sodium hydroxide solution, 2 L of 12.5% sodium hydroxide solution, 1 L of sodium hydroxide solution. . The reaction mixture is then distilled on a Goodlow column with a size of 308 mm, to obtain the fractions shown in Table 2. 12. The resulting product was characterized by GLC, NMR, IR and mass spectrometry as a mixture of compounds of the general formula, where it3o-C U-f. Example 10. Preparation of isobutyric derivative of diisoamylene. In the reaction flask with a capacity of 5 l, equipped with a def. Pegmator, ka7
    a funnel, a thermometer, ter. 953 g (6.0 mol) of eobutyryl anhydride and 105 ml (0.86 mol) of boron trifluoride etherate are added by sealed with a heating jacket, a cooling bath and a device for flushing with nitrogen. The reaction mixture is heated to 65 ° C for 30 minutes, 1725 ml (8.6 mol) of diisoamylene, added as in Example 1, are added. The reaction mixture is then heated to 6365 ° C and maintained at this temperature for 12 hours.
    The reaction mixture is cooled to room temperature and 82 g of sodium acetate is added to it, after which the reaction mixture is poured into a 5 L separatory funnel and washed with 1 l of water, 1 l of 12.5% aqueous sodium hydroxide solution, 1 5% sodium hydroxide solution, 1 liter of 12.5% sodium hydroxide solution, 1 liter of saturated sodium chloride solution.
    Then the organic layer is dried over anhydrous sulfate; sodium and distilled on a Goodlow column (305 mm) to obtain the fractions shown in Table 2. 13.
    Using GLC, NMR, IR and mass spectrometry, the resulting product was characterized as a mixture of compounds of the general formula, where R K3o is C} lj,
    Example 11. Preparation of n-butyryl diisoamylene derivative.
    In the reaction flask with a capacity of 5 l equipped with an electric stirrer,
    942688
    A thermometer, an additional funnel tube, a refrigerator, a heating jacket, and a nitrogen purge device are charged with 5 55 ml of 70% methanesulfonic acid and 30 g of phosphorus pentoxide. The reaction mass is heated exothermically and, in 10 minutes, AOO ml of n-butyric anhydride is added. The reaction mixture is held at 65 G. After 40 minutes, the mixture is kept at 400 ° C, and 400 ml of diisoamylene, obtained analogously to example 1, is added to the reaction mixture. The reaction mixture was stirred at 84 ° C for 4 hours.
    The reaction mass is then transferred to a separating funnel with an open end with a capacity of 5 gallons (19 liters) containing 2 liters of water. The reaction mixture is washed with 1 L of 12% sodium hydroxide water, 1 L of a saturated aqueous solution of sodium chloride w
    Then, the reaction mass is distilled on a Good Silver Silver Mir pop column with a size of 30.5 cm, and the product described by these ga, NMR, IR and mass spectrometry is obtained as a mixture of compounds of the general formula, where.
    In tab. 14 shows the organolectic properties of compounds of the general formula.
    The proposed method allows new scented and aromatic substances that can be used as fragrances, aromatic and flavoring agents.
     .Table
    one
    2 3 4
    161,100,191,189
    62/83
    30/65
    8A 68 68 69 69 71 70 71
    85
    87
    87
    88
    88
    91
    95 73
    106
    80
    142 80 80
    220
    /five
    30.8
    9: 1
    52.8 9: 1
    34 9: 1
    43 9: 1
    34 9: 1 A: 1
    41 A: 1
    36.5 4: 1
    42
    42.5 4: 1 4: 1
    39 4: 1
    50.8 4: 1
    24
    T a b l and c a 3
    Table 5
    Table 7
    Table 9
    17 Table 10
    18
    П94268
    TABLE II
    Table 12
    Fruit, woody and amber fragrance
    Sweet,
    fruit,
    floral,
    woody,
    amber
    aroma
    Fruit,
    woody
    aroma
    T a b ti and p a 13
    Table 14
    Woody,
    citrus,
    floral,
    aroma with
    woody,
    citrus,
    flower
    by taste
    Fruit aroma and taste, both before and during smoking in the main and side stream
    Long acting, moist, deep, warm, woody, vetiver-like fruit flavor
    Warm, woody, amber scent with a high patchouli tone and mint overtone
    Like
    igor / horse by 8 ky amber woody (sandalwood-like) fragrance
    ,
    Sweet, woody, fruity, vetiver-like, aroma with pleasant, similar to burnt sugar nuance
    Long-lasting, strong woody fragrance complete form
    Continued. 14
    Fresh woody, oriental, camphor aroma before smoking and wood-like aroma and taste when smoking in the main as well as in the sidestream
    A floral, ionic, incense-like, and oriental fragrance with an ionic and similar oriental flavor profile.
    Ion-like and Oriental-like flavor and taste profile with a hint of bitterness.
    Burnt sugar-like pineapple flavor and flavor profile
    权利要求:
    Claims (1)
    [1]
    The method of producing derivatives diisoamylene General formula
    "5- ^ ·
    where one of the dashed lines indicates a carbon-carbon double bond, each of the other dashed lines means a simple carbon-carbon bond, and K is a C ^ -C ^ lower alkyl, characterized in that 2-methyl-2-butene is dimerized to the presence of an acid catalyst followed by acylation with
    the resulting diisoamylenes "
    new acyl anhydride in the presence of Lew- - Isa acids or a proton acid as a catalyst at 60 - (yoke
    80 C and distillation of the target product Λ
    ; that AT
    C ©
    and"
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    法律状态:
    优先权:
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    US06/184,132|US4321255A|1980-09-04|1980-09-04|Use of branched ketones in augmenting or enhancing the aroma or taste of foodstuffs, chewing gums, toothpastes or chewing tobacco|
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