• 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:
    Compounds of the general formula (I) are potent sweeteners, especially 4,1',6'-tribromo-4,1',6'-trideoxygalactosucrose: in which R1 represents a chlorine or bromine atom; R2 and R3 respectively represent a hydroxy group and a hydrogen atom or a hydrogen atom and a chlorine or bromine atom; R4 represents a chlorine or bromine atom; at least one of R1, R3 and R4 representing a bromine atom.
    公开号:SU1241996A3
    申请号:SU823446250
    申请日:1982-05-21
    公开日:1986-06-30
    发明作者:Джексон Грахам；Ральф Дженнер Майкл；Ахмед Кан Риаз
    申请人:Тейт Энд Лайл,Паблик Лимитед (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing new sucrose derivatives of the general formula
    BUT
    R,
    L p i / - p V-U 1 p
    EV ..
    R / V /
    BUT he (1
    where R and Ra are respectively a hydroxy group and hydrogen or hydrogen and chlorine or bromine;
    Ra is chlorine or bromine 5 Ri (is chlorine or bromine, which are sweeteners.
    The purpose of the invention is to obtain new sucrose derivatives with greater sweetening power compared to sucrose.
    Example 1. 4,., 6-tribromo-4,1, 6 -trideoxygalactosucrose 4,1, 6 -tri-O-methanesulfonylsaccharose for-pentaacetate was prepared by a known method.
    Pentaacetate (5 g) is dissolved in phosphoric acid hexamethyltriamide (100 ml), then treated with lithium bromide (5 g) for 10 days. For further processing, the reaction mixture is injected into a mixture of ice with
    20
    25
    thirty
    1--4,1, 6-trideoxygalactosucrose, 2,3,4, 6,3, 4 -penta-0-acetylsucrose was obtained by a known method.
    Pentaacetate (27.6 g) and triphenylphosphine (78.6 g 6 molar equivalents) are dissolved in pyridine (300 ml) at room temperature, after which the mixture is cooled to OC. Next, add four-bromide carbon (50 g, 3 molar equivalents (ME), and the mixture became dark). The mixture is then heated at 75 ° C, 1/2 h, and methanol (50 ml) is added — iOT and the resulting solution is evaporated to a syrup density. This syrup is dissolved in dichloromethane (200 mp) and the resulting solution is washed successively with dilute hydrochloric acid, water and an aqueous solution of sodium bicarbonate until neutral. Then the dichloromethane solution is dried by pap, diluted with sodium sulfate and concentrated to dryness, the residue
    water; The resulting precipitate is filtered off with diethyl ether (200 ml).
    The mixture is boiled and dissolved in diethyl ether. The ether solution is then dried over sodium sulfate and concentrated to a solid. After that, the obtained solid material is subjected to reaction with a mixture of acetic anhydride and pyridine (5 ml in 50 ml) and the reaction mixture is again evaporated to dryness. Then the complete acetylated product is purified by chromatography on a column of silica gel, and a mixture of diethyl ether with a light hydrocarbon fraction (1: 1) is used for washing from the adsorbent. The structure of the resulting 4, l, b, tribrom40
    50
    -4.1 .b-trideoxyhalacto-sucrose-pentaacetate was confirmed; H-NM1 and mass spectrometry was confirmed.
    Tribromopentaacetate (1 g) in methanol (10 ml) is treated with metha nate cations: three to reach. After 4 hours, 371/373/375 (a); kept at room temperature, the reaction mixture is examined according to
    The crystalline ospin-o1: sid filter is concentrated., Prod from ethanol, which is –4.1, 6 -trideoxy Pentaacetate, (18.5 g confirmed by
    h /
    magnetic resonance
    4.84 (d, 3, d 3, 10 10, 6,
    5.11 (t, -l ;, 6, 8.3.-8.4l (l5H, 5) The data of the mass spec (a) mark 1,: 2: hexopyranosyl-roll 1: 3 doublet at
    - 9 - -tj U
    5.37 (g, E ,,,, 5.19 (g, 1, .4 5.86 (g, l.f 4.77 (d, 1st
    351/353 (b); 311/313/315 (a);
    1241996
    thin layer chromatography method
    (dichloromethane-methanol 4: 1), which showed the presence of a slow-moving product. The solution is neutralized with an ionomeo exchange resin grade .Amberlust 15 {H), filtered and concentrated to dryness, which yielded 4,1, 6-three bromine 4, 1, 6-trideoxygalactosucrose 0.65 g, 88%, 2 (with 13
    10 acetone),
    Etc
    and m 2. 2. 4.1. , 6-triangle
    five
    0
    1--4,1, 6-trideoxygalactosucrose, 2,3,4, 6,3, 4 -penta-0-acetylsucrose was obtained by a known method.
    Pentaacetate (27.6 g) and triphenylphosphine (78.6 g 6 molar equivalents) are dissolved in pyridine (300 ml) at room temperature, after which the mixture is cooled to OC. Next, add four-bromide carbon (50 g, 3 molar equivalents (ME), and the mixture became dark). The mixture is then heated at 75 ° C., 1/2 hour, adding iOT methanol (50 ml) and the resulting solution evaporated to a syrup density. This syrup is dissolved in dichloromethane (200 mp) and the resulting solution is washed successively with dilute hydrochloric acid, water and an aqueous solution of sodium bicarbonate until neutral. Then the dichloromethane solution is dried by pap, distilled with sodium sulfate and concentrated to dryness, the residue is stirred
    0
     Cations J: 371/373/375 (a);
    Crystalline precipitate of triphenylphosphine-o1: sid is filtered off, the filtrate is concentrated., The product is crystallized from ethanol to give 4,1,6-tribromo-4,1, 6-trideoxygalactosucrose Pentaacetate, (18.5 g, 49%) . The structure is confirmed by N nuclear data.
    h /
    magnetic resonance;
    4.84 (d, 3, d 3.5 Hz, H-1); 10.0 Hz, H-2); 10.0 Hz, H-3); , 5 Hz, H-4); 6.0 Hz, H-3);
    5.11 (t, -l ;, 6.0 Hz, H-4); 8.3.-8.4l (l5H, 5-OAc) The data of the mass spectral analysis (a) mark 1,: 2: 1 received due to the hexopyranosyl cation and (b) mark the 1: 3 doublet due to ketopyranosyl 9 - -tj U
    5.37 (g, E ,,,, 5.19 (g, 1, .4 5.86 (g, l.f 4.77 (d, 1st
    ionsJ: 371/373/375 (a);
    351/353 (b); 311/313/315 (a);
    312419964
    291/293 (b); layered chromatography showed at 231/233 (b); the presence of a homogeneous product. 189/191 (b) is added to the cooling;
    4,1, 6-tribrom-4,1,6-trideoxy methanol, which is then evaporated.
    galactosucrose-pentaacetate (5 g) is dissolved in methanol (50 ml) and treated with 1N sodium methoxide to. After 4 h at room temperature, the solution is neutralized with Amberlyst 15 ion exchange resin (), filtered and concentrated to dryness, which gives 4,1, 6-tribrom-4,1, b-trideoxy galacto-sucrose as a dry syrup, + +75 , 2 (with 1.3 acetone.). In the last example, the compound is called TBS.
    PRI me R 3. 4-bromo-1, b-dichloro-4,1, 6-trideoxy galactosaccharose. (1) 2,3,6,3,4 -penta-0-acetyl- - 4,1,6-dichloro-1,6-dideoxy saccharose.
    A solution of 2,3,6,3,4 -penta-0-ace; tipsaharose (16.6 g) in pyridine (100 ml) is treated with triphenylphosphine (26.2 g) (4 me), which gives a clear solution with room temperature. After cooling to, carbon tetrachloride (9.2 g, 2 me) is added and the stirred mixture is heated to 70 ° C for 1.5 hours. Thin layer chromatography showed that most of the product corresponds to the desired compound. To the cooled reaction mixture is added methanol which is then evaporated. The residue is dissolved in dichloromethane and the solution is washed with water, 1 M hydrochloric acid, saturated sodium bicarbonate and water and then dried, filtered through activated carbon and evaporated. go round The resulting syrup is stirred with ether for 1 hour and the triphenylphosphine oxide crystalline precipitate.
    -filtered. The filtrate is evaporated and washed from the column with silica gel with a mixture of ether and kerosene (1: 1), which gave a 1,6-dichloro derivative (6.6 g, 37%).
    (2) -Bromination to obtain 4-bromo-1, 6-dichloro-4,1, 6-trideoxy-galactosucrose-penta-acetate. A solution of dichloro-derivative (6.6 g) in pyridine (70 g) is worked up with triphenylphosphine (8.7 g, 3 me), then cooled before and carbon tetrabromide (5.6 g, 1.5 me) is added. The reaction mixture is heated to within 2 h, after which the tone 30
    5 The residue is treated as described in example 1. 4-bromo-1, 6 -dichlorop-4, 1. , 6 -trideoxygalactosucrose pentaacetate obtained by crystallization from ethanol, recrystallization yielded 5.2 g (71%). (3) De-acetylation. A solution of penta-acetate (5.2 g) in methanol (50 ml) is treated with an I M solution of sodium ethylate in methanol
    15 to pH ... and at room temperature for 3 hours. The solution is neutralized with Amberlust 15 (H) resin, filtered and evaporated to give 3.3 g (95%) of 4-bromo-1 -, 6-dichloro-4 , 1, 6 -tridek-.
    20 sigalactosachorases in the form of syrup. , 2 ° (c 1.0 NgO).
    PRI me R 4. 4-chloro-1, 6-dibromo-4,1,6-trideoxygalactosucarose.
    25 A mixture of 2,3,6,3, 4 -penta-0-acetyl sucrose (50 g) and trityl chloride (JOO g of about 75% purity) in pyridine (400 ml) is heated
    at 80 for 8 hours. The reaction mixture is poured into water, after which the water is removed from the precipitate by decanting. The precipitate washed with water is dissolved in dichloromethane. The solution is washed with 1 M hydrochloric acid and saturated aqueous sodium bicarbonate solution, then dried, filtered through activated carbon and evaporated. The residue is taken up in methanol, from where tritanol is crystallized. The precipitate is filtered off and the filtrate is evaporated. The residue is then dissolved in 300 ml of pyridine and mixed with molecular sieves (0.4 mm for 2 hours). The sieves are filtered, triphenylphosphine (50.2 me), then carbon tetrachloride (15 ml, 1.5 me) is added to the pyridine solution at room temperature. The mixture is heated to 70 for 1 1/2 hours, then cooled. Methanol (20 ml) was added and the mixture was evaporated. The residue is dissolved in dichloromethane, the solution is washed with 1 M hydrochloric acid, an aqueous solution of bicarbonate, then dried, filtered through 55 activated carbon and evaporated. The residue is taken up in ether and the crystalline residue of triphenylphosphine acid is filtered off.
    35
    40
    50
    0
    5 The residue is treated as described in example 1. 4-bromo-1, 6 -dichlorop-4, 1. , 6 -trideoxygalactosucrose pentaacetate was obtained by crystallization from ethanol, recrystallization gave 5.2 g (71%). (3) De-acetylation. A solution of penta-acetate (5.2 g) in methanol (50 ml) is treated with an I M solution of sodium ethylate in methanol
    5 to pH ... and at room temperature for 3 hours. The solution is neutralized with Amberlust 15 (H) resin, filtered and evaporated to give 3.3 g (95%) 4-bromo-1 -, 6-dichloro-4 , 1, 6 -tridek-.
    0 sigalactosucrose in the form of syrup. , 2 ° (c 1.0 NgO).
    PRI me R 4. 4-chloro-1, 6-dibromo-4,1,6-trideoxygalactosucarose.
    5 A mixture of 2,3,6,3, 4 -penta-0-acetyl sucrose (50 g) and trityl chloride (JOO g of about 75% purity) in pyridine (400 ml) is heated
    at 80 for 8 hours. The reaction mixture is poured into water, after which the water is removed from the precipitate by decanting. The precipitate washed with water is dissolved in dichloromethane. The solution is washed with 1 M hydrochloric acid and saturated aqueous sodium bicarbonate solution, then dried, filtered through activated carbon and evaporated. The residue is taken up in methanol, from where tritanol is crystallized. The precipitate is filtered off and the filtrate is evaporated. The residue is then dissolved in 300 ml of pyridine and mixed with molecular sieves (0.4 mm for 2 hours). The sieves are filtered, triphenylphosphine (50.2 me), then carbon tetrachloride (15 ml, 1.5 me) is added to the pyridine solution at room temperature. The mixture is heated to 70 for 1 1/2 hours, then cooled. Methanol (20 ml) was added and the mixture was evaporated. The residue is dissolved in dichloromethane, the solution is washed with 1 M hydrochloric acid, an aqueous solution of bicarbonate, then dried, filtered through activated carbon and evaporated. The residue is taken up in ether and the crystalline residue of triphenylphosphine acid is filtered off.
    five
    0
    0
    Then, the contents of the ether solution are absorbed with glacial acetic acid (750 ml) and heated to about 110 ° C, water (15 ml) is added and the mixture is heated at about 120 for about 1 hour. The mixture is evaporated and dried) | Lenia and temperature
    pe below bb, then distilled together with toluene. The tritanol contained in the mixture is crystallized from the methanol solution and the remaining product is treated according to the method of column chromatography on silica gel. Ether is used to wash out the adsorbent, yielding 4-chloro-4-deoxyhalo-sucrose penta acetate (6.2 g, 12%). To a solution of the above pentaacetate (6.2 g 1 me) and triphenylphosphine (11.4 r, j 4 me) in pyridine (10 ml), carbon tetrabromide (7.3 g, 2 me). This mixture is heated at 80 s for 1 h. The mixture is cooled for 1 h and triphenylphosphine (5.7 g) and carbon tetrabromide (3.7 g) are additionally added to the reaction mixture. To complete the reaction, the mixture is then heated at 80 ° C for 1 hour. The mixture is cooled and methanol (20 ml) is added; After packing the mixture, the residue is dissolved in dichloroethane. The solution is washed with 1 M:; cr; hydrochloric acid and an aqueous solution of sodium bicarbonate, after which it is dried, filtered through activated carbon and evaporated. The residue is taken up in ether, from which the crystalline precipitate of triphenylphosphine oxide is filtered off. The filtrate is evaporated, the residue is dissolved in ethanol, which gives 5.9 g (80%) of 4-chloro-1, 6 -dibrome derivative in the form of pentaacetate in the form of crystals. Recrystallization from ethanol gives 5.1 g of purified pentaacetate.
    This material (1.5 g) is deacetyly-ruled using sodium methoxide in methanol at a pH of about 9.5 and at room temperature. The solution is neutralized with Amberlyst 15 H resin, then filtered and evaporated to give 4-chloro-1, 6-dibrom-4,1 6-three deoxigalactose}, 0 g (95%) f + +52.3 (0 , 7 water), t.p. 87 + 93 C (times.).
    Primer, 1, 6 -dibrom, 1, 6-dideoxygalactosucrose, 2,3,6,3, penta-0-acetyl-sucrose (13.8 g) days;
    0
    :five
    O
    five
    stitched by the method, similarly to example 4, with the use of 26.4 g (4 me) triphenylphosphine and about 16.6 g (2-me) carbon tetrabromide in
    / h 0
    pyridine (100 ml) at 70 ° C. The sequence of the reaction was monitored by thin layer chromatography. The product is isolated and purified according to example 4, which gives 4.1 g of product. Recrystallization from ethanol-ethyl acetate-ether to give 2.3 g (41%). .
    G. T (..ig.,
    ljp + 71, 1 (, 4 water). EXAMPLE 6: Reproduce the procedure in Example 1, using AL penta-benzoate, 6-tri-0-methanes lofonyl-sucrose, obtained by the method, analogous to the n-1 method Hough and Mufti instead of pentaacetate, and get bromo-4,1,6-trideoxygalactosucrose with the same yield /
    II p and me R 7. Reproduce the method of example. 1 except that, instead of the three 0-methanesulfonyl derivative, 4-: lor-1, 6-di-O-methanesulfonyl lactosucrose and derived from 4-chloro-4-deoxygalactosucrose are used (Sag-hygrate Research ) 40/1975 / 285-298 / no method: /, similar to the method of Hough U Mufti (sms above); and get 4-chloro - 1 b -dibrom-A 51, 6-trideoxygalactosucrose.
    PRI me R 8, sweetener tablets for drinks.
    Each tablet contains 5 mg TBC in combination with. disintegrating base for tablets (about 60 mg). The base contains sucrose gum arabic and magnesium stearate. According to the degree of sweetness, each tablet is equivalent to approximately 4.5 g of sucrose.
    PRI me R 9. A sweetening powdered agent having the same degree of sweetness as the equivalent volume of sucrose (granulated sugar) is obtained by displacement,
    , the following ingredients and spray dried to obtain a powder with a bulk weight of 0.2 g / cm. A solution of maltodextrin contains; 1.25 g with a dry weight of 222.2 g. The resulting composition has a degree
    : sweets equivalent to about 2 kg of sugar.
    Bromo-derivatives of formula (1), corresponding to the proposed invention / 1241996
    This can be used in the same way as sweetening as chlorosacrose.
    In general, bromine is a derivative of the general formulas (O, as defined above, is extremely sweet, if at least one of E and N. means bromine atoms, then the derivatives are each at least as sweet as the corresponding chlorine - analogue. If R and Rj mean bromine atoms, the degree of sweetness exceeds that of chlorine analogues.Read examples of this situation are given in the table, where degrees of sweetness are registered in comparison to about 8% by weight of sugar-sugar solution, Shl.
    Editor Yu, Sereda
    Compiled by I. Fedoseeva
    Tehred I.Popovich Proofreader O, Lugova
    Order 3619/60 Circulation 343Subscription
    VNIIPI USSR State Committee
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
    Production and printing company, Uzhgorod, st. Project, 4
    All compounds listed in the table have a Bbmie of 1 g / kg.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING DERIVATIVES
    SUGAROSES of the general formula where and R z are respectively an oxy group and hydrogen or hydrogen and chlorine or bromine;
    Rj is chloro or bromo;
    Rt is chlorine or bromine, and at least one of R 2 , Rj and Rz is bromine, characterized in that the compound of general formula wherein X is an acetoxy protecting group or a benzoyloxy group;
    Y / and Yij — chlorine or bromine, an oxy group which may be protected in the form of a trityl group, or a leaving group in the form of a methanesulfonyloxy group:; ',
    Υρ. - an oxy group or a leaving group in the form of a methanesulfonipoxy group;
    Yj is hydrogen; or Yi is hydrogen;
    Yj is chlorine or bromine;
    at least one of the groups Yq ,, Y g and Υ ({is an oxy group or a leaving group, is reacted with a booking agent containing carbon tetrabromide with triphenylphosphine, if at least one of the groups X,, and Yz, is an oxy group, and the rest is chlorine and bromine, at 7О-8О Р С in pyridine, or with lithium bromide, if at least one of the groups Y ^, Υ 2 and Υ ^ is a methanesulfonyloxy group ·, at 90 С hexamethylphosphorotriamide.
    SU., "1241996 AZ
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB8115838|1981-05-22|
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