Method for preparing allolactose

A technology of glucofuranose and acetyl, which is applied in the field of allolactose preparation, can solve the problems of poor reproducibility, impossibility of purification, and low yield, and achieve the effects of good stereoselectivity, easy purification, and high yield

Inactive Publication Date: 2014-03-26
CHINA AGRI UNIV
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  • Abstract
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AI Technical Summary

Problems solved by technology

[0004] The synthesis methods disclosed in the above-mentioned documents have the following problems: First, the chemical synthesis methods reported in the existing literature have long routes (8 to 15 steps of reaction), low yields (the highest total yield is 12%), and reproducibility Not good (the bromogalactose or chlorogalactose donors are not stable enough to be purified), separation and purification are difficult (the impurity content is too large), and it is not suitable for the large-scale preparation of isolactose; second, the existing The yield of allolactose synthesized by enzymatic method is extremely low, and the obtained allolactose is at the milligram level, which cannot be used for the large-scale synthesis of allolactose

Method used

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  • Method for preparing allolactose
  • Method for preparing allolactose
  • Method for preparing allolactose

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0067] Synthesis of compound shown in embodiment 1, formula IV

[0068]

[0069] Dissolve the compound (7.86 g, 30.0 mmol) shown in Formula II in 100 mL of dry CH 2 Cl 2 Add Py (12mL, 150.0mmol), cool in an ice bath to -10°C, add AllocCl (3.55mL, 33mmol) in 40mL of CH 2 Cl 2 Solution. Remove the ice bath after the dropwise addition, and stir at room temperature for 2 hours. TLC (3:1, petroleum ether-ethyl acetate) detected that the reaction was complete. The reaction system was sequentially washed with 1M hydrochloric acid and saturated NaHCO 3 solution, washed with saturated brine, CH 2 Cl 2 Extraction, anhydrous Na 2 SO 4 Drying, concentration, and column chromatography (4:1, petroleum ether-ethyl acetate) separated the compound represented by formula IV (10 g, yield 97%).

[0070] Structural Confirmation Data:

[0071] [α] D 25 =+108°(1g / 100mL, CHCl 3 ), 1 H NMR (CDCl 3 ,300MHz)δ:1.31,1.51(2s,6H,CMe 2 ),2.13(s,3H,COCH 3 ),2.94(d,J=4.5Hz,1H,OH),3.90(m,1H,H...

Embodiment 2

[0073] Embodiment 2, the synthesis of compound 2 (belonging to a kind of general formula compound V)

[0074]

[0075] Dissolve the compound shown in Formula IV (10.4g, 30mmol) in 60mL of dry pyridine, add BzCl (4.2mL, 36mmol) dropwise under ice bath, stir for 30 minutes under ice bath after the addition, and then place the system at room temperature After reacting for 5 hours, TLC (3:1, petroleum ether-ethyl acetate) detected that the reaction was complete. The reaction system with CH 2 Cl 2 Dilute with 1M hydrochloric acid, saturated NaHCO 3 solution, washed with saturated brine, CH 2 Cl 2 Extraction, anhydrous Na 2 SO 4 Drying and concentration column chromatography (4:1, petroleum ether-ethyl acetate) separated to give light yellow viscous liquid 2 (13.5g, yield 100%).

[0076] Structural Confirmation Data:

[0077] [α] D 25 =+120°(1g / 100mL, CHCl 3 ), 1 H NMR (CDCl 3 ,300MHz)δ:1.31,1.52(2s,6H,CMe 2 ),2.01(s,3H,COCH 3 ),4.40(dd,J=5.0Hz,12.2Hz,1H,H-4),4.51(...

Embodiment 3

[0079] Embodiment 3, the synthesis of compound 3 (belonging to a kind of general formula compound VI)

[0080]

[0081] In a 250mL round bottom flask, dissolve compound 2 (9g, 20mmol) in 200mL methanol-ethyl acetate (volume ratio, 1 / 2) solution, add CH to the system 3 COONH 4 (30.8g, 400mmol), cooled in an ice bath to –10°C, and quickly added PdCl to the system 2 (35mg, 0.2mmol), NaBH 4 (1.52g, 40mmol). TLC (2:1, petroleum ether-ethyl acetate) detected that the reaction was complete, and it took 1 hour in total. The reaction solution was concentrated under reduced pressure to remove methanol and tetrahydrofuran. The reaction system with CH 2 Cl 2 Diluted, extracted with saturated saline, anhydrous Na 2 SO 4 Drying and concentration column chromatography (4:1, petroleum ether-ethyl acetate) separated to give light yellow viscous liquid 3 (6.9 g, yield 95%).

[0082] Structural Confirmation Data:

[0083] [α] D 25 =+88°(1g / 100mL, CHCl 3 ), 1 H NMR (CDCl 3 ,300M...

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Abstract

The invention discloses a method for preparing allolactose. According to the method, 1,2-O-(1-methyl ethylidene)-3-O-acetyl-alpha-D-furan glucose is used as an initial raw material, a glycosyl receptor 1,2-O-(1-methyl ethylidene)-3-O-acetyl-5-O-benzoyl-alpha-D-furan glucose midbody is obtained through three steps of reaction, the yields and the purities of each step of reaction are all high (the yield is respectively 97%, 100% and 95%, and the purities are respectively 99.5%, 99.2% and 99.8%). Therefore, midbodies IV and V can be applied to next step of reaction without being purified in large-scale preparation, a compound formula VII is obtained by coupling a midbody formual VI and a midbody formula V, the reaction condition is obtained through optimization, the yield is high (80%), the stereoselectivity is good (no isomer is detected), purification can be easily achieved, the total yield that a disaccharide formula VII is prepared from a compound formula II through four steps of reaction is 74%, the purity is 99.8%, and the purity of a final product of the invention is high, that is, the purity is not less than 98%.

Description

technical field [0001] The invention relates to a preparation method of allolactose. Background technique [0002] Allolactose is an isomer of lactose, and its chemical structure is β-D-galactosyl-(1→6)-D-glucose, which is a reducing disaccharide. Under the action of β-galactosidase, lactose can be converted into allolactose, which is the inducer of the lactose operon and plays a very important biological role in the metabolic process of bacteria. For example, in Escherichia coli, allolactose is involved in regulating the activity of the lactose operon, which contains three structural genes (LacZ, LacY and LacA), which are mainly responsible for absorbing and hydrolyzing lactose as a carbon source for the life activities of Escherichia coli. If lactose is absent in the bacterial growth environment, the repressor protein binds tightly to a short DNA sequence (called the lactose operator) located downstream of the promoter near LacZ. The repressor protein bound to the operat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07H1/00C07H13/12C07H13/08C07H3/04
Inventor 张建军姜锐梁晓梅王道全
Owner CHINA AGRI UNIV
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