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Method for synthesizing gamma-carbonyl ester compound by gamma-hydroxied gadoleic acid ester

A technology of hydroxyalkenoate and compound, applied in the field of organic intermediate synthesis, can solve the problems of respiratory system damage, carcinogenicity, difficult storage and transportation, etc., and achieves the effects of wide application, cost reduction, and avoidance of transition metal residues

Inactive Publication Date: 2011-08-10
LANZHOU UNIVERSITY
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  • Abstract
  • Description
  • Claims
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AI Technical Summary

Problems solved by technology

But the application of this method has been subjected to the serious restriction of reagent used---diazomethane: (a) this method must just can obtain gamma-carbonyl ester compound through two-step reaction by gamma-hydroxyalkenic acid ester; (b) two-step reaction The middle esterification step requires the use of highly toxic and explosive diazomethane as an additional esterification reagent. The boiling point of this reagent (-23°C) is lower than room temperature, and it is not easy to store and transport. It can occur when heated, impacted or subjected to frictional vibration Explosion has serious damage to the respiratory system and can strongly cause cancer. It belongs to Class I explosives and Class II organic poisons, so this method has great limitations; (c) the strong base KOH used in this method It also has obvious limitations in the scope of its substrate application

Method used

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  • Method for synthesizing gamma-carbonyl ester compound by gamma-hydroxied gadoleic acid ester
  • Method for synthesizing gamma-carbonyl ester compound by gamma-hydroxied gadoleic acid ester
  • Method for synthesizing gamma-carbonyl ester compound by gamma-hydroxied gadoleic acid ester

Examples

Experimental program
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Effect test

Embodiment 1-10

[0026] Examples 1-10: Adding Mg(OMe) to a round bottom flask 2 (10~80mol%, 0.033M methanol solution) and catalyst IIa (IIa: R 3 =R 4 =Me, i.e. tetramethylethylenediamine, abbreviated as TMEDA, 0~100mol%), then add (Z)-γ-hydroxyalkenoate compound Ia (Ia: R 1 =C 7 h 15 , R 2 =Me) (0.2mmol), stirred at room temperature for 0.5 to 3 hours, after the thin plate chromatography detection reaction was completed, concentrated under reduced pressure to remove excess methanol, then added 5% hydrochloric acid to quench, the aqueous phase was extracted three times with ethyl acetate, combined The organic phase was washed with saturated brine, then dried over anhydrous sodium sulfate, concentrated to dryness under reduced pressure, and purified by column chromatography (petroleum ether: ethyl acetate = 12:1 ~ 9:1) to obtain a colorless liquid which was γ- Carbonyl ester compound IIIa (IIIa: R 1 =C 7 h 15 , R 2= Me). Its chemical formula represents as shown in (1):

[0027]

[...

Embodiment 11-15

[0037] Embodiment 11-15 product---gamma-carbonyl ester compound (IIIb) NMR and mass spectrum: 1 H NMR: δ7.95 (1H, s, ArH), 7.85-7.87 (1H, d, J = 7.5Hz, ArH), 7.53-7.56 (1H, d, J = 7.8Hz, ArH), 7.39-7.47 ( 1H, m, ArH), 3.71(3H, s, MeO), 3.27-3.33(q, J=6.6Hz, 2H), 2.75-2.82(q, J=6.6Hz, 2H). 13 C NMR: δ196.8, 173.1, 138.1, 135.0, 133.1, 130.0, 128.2, 126.1, 51.9, 33.5, 27.9. EI-MS (m / z): 226 (M + ), 195 (M + -31), 139(M + -87), 111 (M + -115).

Embodiment 16

[0038] Example 16: Addition of Mg(OMe) to a round bottom flask 2 (67mol%, 0.033M methanol solution) and TMEDA (50mol%), then add (E)-γ-hydroxyalkenoate compound (0.2mmol), stir at room temperature for 48 hours, after the thin plate chromatography detection reaction is completed, decompression Concentrate to remove excess methanol, then add 5% hydrochloric acid to quench, the aqueous phase is extracted three times with ethyl acetate, the combined organic phase is washed with saturated brine, then dried with anhydrous sodium sulfate, concentrated to dryness under reduced pressure, and purified by column chromatography (Petroleum ether: ethyl acetate = 12:1-9:1) to obtain a colorless liquid which is the γ-carbonyl ester compound (the product is the same as in Example 17).

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Abstract

The invention relates to a method for synthesizing gamma-carbonyl ester compound by gamma-hydroxied gadoleic acid ester. A gamma-hydroxied gadoleic acid ester compound shown as a formula I is reacted at certain temperature in organic solvent in the presence of catalysts of an alcoxyl alkali-earth metal compound and a diamine compound shown as a formula II, and reaction products are quenched, separated and purified to obtain the gamma-carbonyl ester compound III. Through one-step catalysis reaction only, various different substituted gamma-carbonyl ester compounds can be quickly synthesized by the gamma-hydroxied gadoleic acid ester at high yield. The catalysts are wide in sources, cheap and readily-available and have stable chemical properties for light and heat, and transition metals and highly toxic products can be prevented from being used and generated. Compared with the prior art, the method has the advantages of mild reaction condition, obvious operating safety, and obviously widely application range.

Description

technical field [0001] The invention belongs to the synthesis of organic intermediates, and relates to a preparation method for synthesizing gamma-carbonyl ester compounds from gamma-hydroxyalkenoate esters. Background technique [0002] As a necessary means for the development of new drugs, the development of new chemical reactions and new reagents are the two most important research contents in organic chemistry. With the increasingly serious problem of drug safety, residues of transition metals (especially heavy metals) in drugs have become one of the key problems that need to be solved urgently in the pharmaceutical industry. Therefore, avoiding the use of transition metals has important practical significance for drug synthesis. The allyl alcohol rearrangement reaction can directly obtain saturated carbonyl compounds, which can avoid environmental pollution caused by cumbersome steps such as oxidation (reduction) and reduction (oxidation) reactions of allyl alcohol com...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/716C07C67/313C07B41/06C07C69/738C07D307/46
Inventor 王锐林利李阿妮
Owner LANZHOU UNIVERSITY
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