Synthesis method of 8-iodine-1-naphthoic acid and application of 8-iodine-1-naphthoic acid in preparation of glycosyl 8-alkynyl naphthoate

By synthesizing 8-iodo-1-naphthoic acid using cheap and low-toxic chemical reagents, the problems of low yield and high cost in the existing technology are solved, and the efficient preparation of glycosyl 8-alkynyl naphthoate is achieved, which is suitable for the efficient construction of sugar compounds.

CN120647526APending Publication Date: 2025-09-16ZHONGSHAN INST FOR DRUG DISCOVERY SHANGHAI INST OF MATERIA MEDICA CHINESE ACAD OF SCI
View PDF 0 Cites 0 Cited by

Patent Information

Application Number
CN202510700771.X
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-05-28
Publication Date
2025-09-16

AI Technical Summary

Technical Problem

The existing preparation methods of 8-iodo-1-naphthoic acid have the problems of low yield, high cost, small scale, and use of toxic reagents. In addition, the commercially available 8-bromo-1-naphthoic acid is expensive, making it difficult to efficiently prepare glycosyl 8-alkynyl naphthoate.

Method used

8-iodo-1-naphthoic acid was synthesized using cheap and low-toxic chemical reagents such as naphthalene dicarboxylic anhydride, R1OH, LiOH, iodobenzene acetate and I2 through photoreaction and temperature-controlled steps. It was then reacted with R2OH in the presence of palladium catalyst and CuI to prepare glycosyl 8-alkynyl naphthoate.

Benefits of technology

The cheap, safe and large-scale preparation of 8-iodo-1-naphthoic acid was achieved, the yield and purity were improved, the synthesis cost was reduced, and the efficient glycosidic bond construction ability was demonstrated in the glycosylation reaction.

✦ Generated by Eureka AI based on patent content.

Smart Images

  • Figure BDA0005424479750000053
    Figure BDA0005424479750000053
  • Figure BDA0005424479750000054
    Figure BDA0005424479750000054
  • Figure BDA0005424479750000061
    Figure BDA0005424479750000061
Patent Text Reader

Abstract

The invention belongs to the field of synthesis, and particularly discloses a synthesis method of 8-iodo-1-naphthoic acid and application of the 8-iodo-1-naphthoic acid in preparation of glycosyl 8-alkynyl naphthoate, the synthesis method of the 8-iodo-1-naphthoic acid comprises the following steps: S1, mixing raw materials including naphthalic anhydride, R1OH and LiOH for reaction, then reacting with iodosobenzene diacetate and I2 under illumination, then removing alkyl, and obtaining 8-iodo-1-naphthoic acid; the 8-iodine-1-naphthoic acid is obtained; according to the synthesis method of the 8-iodine-1-naphthoic acid, cheap and low-toxicity chemical reagents such as lithium hydroxide, iodobenzene diacetate, sodium iodide and iodine are adopted, so that the synthesis cost can be remarkably reduced, the experiment safety is improved, the pollution to the environment is reduced, meanwhile, the 8-iodine-1-naphthoic acid with higher yield and purity is obtained within shorter time, and the method is suitable for industrial production. And the large-scale preparation of the 8-iodine-1-naphthoic acid at a 10-gram level is realized.
Need to check novelty before this filing date? Find Prior Art

Claims

1. A method for synthesizing 8-iodo-1-naphthoic acid, characterized in that: The following steps are involved: S1: Mix and react the raw materials including naphthalic anhydride, R1OH and LiOH to obtain S2: Then make Iodobenzene acetate reacts with I2 under light to obtain S3: Make The reaction generates the 8-iodo-1-naphthoic acid; The R1 is selected from methyl, ethyl or propyl.

2. The synthetic method of 8-iodo-1-naphthoic acid according to claim 1, wherein: The reaction in step S2 has at least one of the following characteristics: (a1) the reaction temperature is 75-90°C; (a2) The reaction time is 1 to 5 hours; (a3) The reaction is carried out under 150-550W tungsten halogen lamp illumination; (a4) The reaction is carried out in the presence of a solvent; the solvent includes acetonitrile.

3. The synthetic method of 8-iodo-1-naphthoic acid according to claim 1, wherein: described The molar ratio of iodobenzene acetate to iodobenzene acetate is 1:(1.4-1.8); and / or, The molar ratio to I2 is 1:(1.25~1.65).

4. The synthetic method of 8-iodo-1-naphthoic acid according to claim 1, wherein: The reaction in step S3 has at least one of the following characteristics: (b1) the reaction temperature is 130-140°C; (b2) The reaction time is 9 to 15 hours; (b3) The reaction is carried out in the presence of NaI and LiI; (b4) The reaction is carried out in the presence of a solvent, which includes pyridine.

5. The synthetic method of 8-iodo-1-naphthoic acid according to claim 4, wherein: In step S3, the molar ratio of NaI to LiI is (1.8-2.2):1; And / or, in step S3, the total amount of NaI and LiI is The molar ratio of substances is (2.5~3.5):

1.

6. The synthetic method of 8-iodo-1-naphthoic acid according to claim 1, wherein: The mixing reaction time in step S1 is 1 to 10 minutes; and / or, the temperature of the mixing reaction in step S1 is 20-35° C.; and / or, in step S1, the molar ratio of naphthalic anhydride to LiOH is 1:(1.3-1.7); And / or, in step S1, the molar ratio of naphthalene dicarboxylic anhydride to R1OH is 1:(20-100).

7. Use of the synthesis method of 8-iodo-1-naphthoic acid according to any one of claims 1 to 6 in the preparation of glycosyl 8-alkynyl naphthoates.

8. A method for preparing glycosyl 8-alkynyl naphthalate, characterized in that: The following steps are involved: (1) synthesizing 8-iodo-1-naphthoic acid by the synthesis method according to any one of claims 1 to 6; (2) reacting the 8-iodo-1-naphthoic acid with R2OH to produce (3) Make and The reaction generates the glycosyl 8-alkynyl naphthoate; R2 is selected from Bn is benzyl, Bz is benzoyl, Ac is acetyl; R3 is selected from Each R4 is independently selected from C 1～10 Alkyl; The glycosyl 8-alkynyl naphthoate is selected from 9. The method for preparing glycosyl 8-alkynyl naphthalate according to claim 8, wherein: The step (3) further comprises the step of adding palladium catalyst and CuI.

10. The method for preparing glycosyl 8-alkynyl naphthalate according to claim 8, characterized in that: described and The molar ratio is 1:(0.1~5).