CN116239554B - Method for preparing gamma-lactone compounds through hydrogenolysis reaction - Google Patents

Method for preparing gamma-lactone compounds through hydrogenolysis reaction Download PDF

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CN116239554B
CN116239554B CN202310013773.2A CN202310013773A CN116239554B CN 116239554 B CN116239554 B CN 116239554B CN 202310013773 A CN202310013773 A CN 202310013773A CN 116239554 B CN116239554 B CN 116239554B
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hydroxyl
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lactone
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CN116239554A (en
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张德旸
张永振
李建锋
刘连才
姜鹏
李金明
黎源
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters
    • B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H

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Abstract

The invention provides a method for preparing gamma-lactone compounds through hydrogenolysis reaction. The hydroxyl-containing gamma-lactone compound is used as a raw material and reacts with a hydrogen donor under the action of an organic phosphonic acid catalyst to obtain the gamma-lactone compound in one step, and the reaction has the characteristics of high yield, obvious application value and the like. Under the catalytic system, the perfume peach aldehyde, coconut aldehyde and propiolactone can be obtained in one step.

Description

Method for preparing gamma-lactone compounds through hydrogenolysis reaction
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for preparing gamma-lactone compounds through hydrogenolysis reaction.
Background
Many gamma-lactones have a unique fragrance. For example, peach aldehyde, i.e., undecalactone, has strong peach and almond-like aromas; coconut aldehyde is propionolactone, and has coconut fragrance; the decalactone has strong coconut and peach-like fragrance. The spices are widely used in edible essence and daily chemical essence, and can also be used in tobacco and feed essence. The most used and sold amounts of lactone perfume at present are peach aldehyde, coconut aldehyde and propiolactone, and the structure is shown as follows:
Although the gamma-lactone compound has good application value, the natural content of the compound is very small, and in order to meet the market demand, the artificial synthesis is a main method at present. However, the existing gamma-lactone compounds have the problems of troublesome synthesis, relatively high cost and the like, and the synthesis of peach aldehyde is used for the following description:
the synthesis of peach aldehyde mainly has 5 routes according to different raw materials. Route 1: heating and dehydrating hydroxy acid and sulfuric acid to prepare the aqueous solution; route 2: the method is characterized in that alpha-olefin and acetic acid are used as raw materials, and cerium, vanadium and other high-valence acetates or manganese acetate are used as oxidizing agents for preparation; route 3: beta, gamma-olefine acid is used as raw material and prepared through acid catalysis cyclization reaction; route 4: the intermediate alpha, beta-olefine acid is synthesized by taking long-chain fatty aldehyde and malonic acid as raw materials, and then the intermediate alpha, beta-olefine acid is prepared through acid catalytic cyclization reaction. The scheme is not a mainstream industrialized route at present due to the problems of strong acid, low yield, higher production cost or complex flow and the like.
At present, most manufacturers adopt a production route for synthesizing peach aldehyde by one step by using n-octanol and acrylic acid or methyl acrylate as raw materials and tert-butyl peroxide as an initiator and adding, lactonizing and dehydrating. But this solution also has a number of problems: 1) Peroxide is used as an initiator in the reaction, so that the safety requirement is high; 2) The industrialized reaction yield is generally about 60-70%, and is relatively low; 3) The operation temperature is 110-140 ℃ generally, and is relatively high; 4) The product contains grease gas to influence the fragrance quality, the fragrance of the product is not easy to reach the standard, the procedures of fragrance reforming and the like are required to be added, and the procedure is complex and more complex.
In short, the current route for synthesizing gamma-lactone compounds such as peach aldehyde has a plurality of defects in industrial production, so that the development of a new route for synthesizing gamma-lactone compounds such as peach aldehyde with high yield and high selectivity has important significance.
Disclosure of Invention
The invention aims to provide a method for preparing gamma-lactone compounds through hydrogenolysis reaction, which has the characteristics of high yield, obvious application value and the like. Under the catalytic system of the invention, the perfume peach aldehyde, coconut aldehyde and propiolactone can be obtained in one step.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
A method for preparing gamma-lactone compounds by hydrogenolysis reaction uses hydroxyl-containing gamma-lactone compounds as raw materials, and the hydroxyl-containing gamma-lactone compounds react with hydrogen donors under the action of an organic phosphonic acid catalyst to obtain the gamma-lactone compounds in one step.
The reaction of the present invention is schematically shown below:
in some particular embodiment schemes, peach aldehyde, coconut aldehyde, and propiolactone may be obtained:
in the invention, the gamma-lactone compound has a structure as shown in formula I:
wherein R 1 is one or more of C1-C40 alkyl, C3-C12 unsubstituted cycloalkyl, C3-C12 substituted cycloalkyl, phenyl, substituted phenyl, benzyl, substituted benzyl, five-membered or six-membered heterocyclic aromatic group containing one or more oxygen, sulfur and nitrogen atoms, and ester group; wherein, the substituent of the C3-C12 cycloalkyl, the substituted phenyl and the substituted benzyl with the substituent can be one or more of C1-C40 alkyl, C1-C40 alkoxy, halogen, nitro, ester group and cyano.
In the invention, the hydroxyl-containing gamma-lactone compound of the raw material has a structure as shown in formula II:
wherein R 1 is the same as R 1 in the above structural formula (I).
In the invention, the hydrogen donor is at least one of formic acid, a compound of formula III and a compound of formula IV, and is preferably a compound of formula III-1:
Wherein R 2、R3 is one or more of C1-C40 alkyl, C3-C12 unsubstituted cycloalkyl, C3-C12 substituted cycloalkyl, phenyl, substituted phenyl, benzyl, substituted benzyl, five-membered or six-membered heterocyclic aromatic group containing one or more oxygen, sulfur and nitrogen atoms, and ester group; r 4、R5 is one or more of C1-C40 alkyl, C3-C12 unsubstituted cycloalkyl and C3-C12 substituted cycloalkyl; wherein the substituent of the C3-C12 cycloalkyl, the substituted phenyl and the substituted benzyl with the substituent is one or more of C1-C40 alkyl, C1-C40 alkoxy, halogen, nitro, ester and cyano.
In the present invention, the organophosphonic acid catalyst is an organophosphonic acid catalyst of formula V, preferably an organophosphonic acid catalyst of formula V-1:
Wherein R 6、R7、R8、R9、R10、R11 is one or more of H, C1-C40 alkyl, C3-C12 unsubstituted cycloalkyl, C3-C12 substituted cycloalkyl, phenyl, substituted phenyl, benzyl, substituted benzyl, five-membered or six-membered heterocyclic aromatic group containing one or more oxygen, sulfur and nitrogen atoms and ester group respectively and independently; wherein the substituent of the C3-C12 cycloalkyl, the substituted phenyl and the substituted benzyl with the substituent is one or more of C1-C40 alkyl, C1-C40 alkoxy, halogen, nitro, ester and cyano.
In the present invention, the reaction may be with or without the addition of a solvent; preferably, when the solvent is added, the solvent is at least one of methanol, ethanol, toluene, benzene, xylene, dichloromethane, dichloroethane, diethyl ether, tetrahydrofuran and ethyl acetate, preferably tetrahydrofuran.
In the present invention, the molar ratio of the organic phosphonic acid catalyst to the hydroxyl group-containing gamma-lactone compound as a raw material is (0.001-0.1): 1, preferably (0.01-0.06): 1.
In the invention, the molar ratio of the hydrogen donor to the hydroxyl-containing gamma-lactone compound in the raw material is 0.5-10:1, preferably 1-1.2:1.
In the present invention, the reaction temperature is 0 to 130 ℃, preferably 50 to 80 ℃; the reaction time is 0.5 to 72 hours, preferably 1 to 3 hours.
Another object of the present invention is to provide a gamma-lactone compound.
The gamma-lactone compound is prepared by adopting the method for preparing the gamma-lactone compound through hydrogenolysis reaction.
Compared with the prior art, the invention has the following positive effects:
(1) The raw material yield is high (up to 98%);
(2) The invention can obtain peach aldehyde, coconut aldehyde and propiolactone through one-step reaction respectively;
(3) The process flow is simple and is easy to industrialize.
Detailed Description
The process according to the invention is further illustrated by the following specific examples, but the invention is not limited to the examples listed but encompasses any other known modifications within the scope of the claims.
Analytical instrument:
1) Nuclear magnetic resonance spectrometer model: BRUKER ADVANCE Ⅲ400,400MHz,CDCl3 is used as solvent;
2) Gas chromatograph: agilent7890, DB-5 separation column, gasifier temperature 300 ℃, detector temperature 300 ℃, temperature ramp program, onset temperature 40 ℃, constant temperature 10min, ramp to 130 ℃ at 5 ℃/min, ramp to 300 ℃ at 20 ℃/min, constant temperature 6min.
Main raw material information:
Hydrogen donor hans ester III-1, III-2, III-3, III-4, bisphenol compound VI-1, VI-2, chemical purity >99%, chongqing FuTENG medical Co Ltd;
4-oxo-undecanoic acid VII-1, 4-oxo-nonanoic acid VII-2, 4-oxo-decanoic acid VII-3, chemical purity is more than or equal to 98%, beijing enokic science and technology Co., ltd;
Methanol, toluene, dichloroethane, tetrahydrofuran, ethyl acetate, methylene chloride, diethyl ether, n-hexane, isopropanol, chemical purity >99.5%, company, aba Ding Shiji;
pyridine, phosphorus oxychloride, sodium chloride, sodium sulfate, 1, 8-diazabicyclo undec-7-ene and ammonium chloride, wherein the chemical purity is more than or equal to 98%, and Ara Ding Shiji Limited company;
concentrated hydrochloric acid, 37% chemical purity, ala Ding Shiji inc;
The main synthesis equipment comprises: three-neck flask, pressure-resistant reaction kettle and constant temperature oil bath pot.
Example i
Compound V-1 was synthesized.
Bisphenol compound VI-1 (1 mol), pyridine (2 mol) and dehydrated ether (300 mL) were added to the flask, the reaction system was cooled to 0℃and POCl 3 (1.4 mol) was slowly added to the reaction system using a dropping funnel, followed by heating and refluxing, continuing stirring and reacting for 13 hours, and the reaction was stopped. Cooled to room temperature, the pyridine hydrochloride solid was filtered off, then washed successively with 4mol/L HCl, saturated brine, dried over anhydrous sodium sulfate, concentrated to remove the solvent, and the residue was recrystallized from n-hexane to give ligand V-1 (yield 96%). The characterization result is: 1HNMR(400MHz,CDCl3 ) Delta 2.33 (s, 6H), 4.0 (s, 1H), 6.80 (d, 2H), 7.30 (d, 2H).
Example ii
Compound V-2 was synthesized.
Bisphenol compound VI-2 (1 mol), pyridine (2 mol) and dehydrated ether (300 mL) were added to the flask, the reaction system was cooled to 0℃and POCl 3 (1.4 mol) was slowly added to the reaction system using a dropping funnel, followed by heating and refluxing, continuing stirring and reacting for 15 hours, and the reaction was stopped. Cooled to room temperature, the pyridine hydrochloride solid was filtered off, then washed successively with 4mol/L HCl, saturated brine, dried over anhydrous sodium sulfate, concentrated to remove the solvent, and the residue was recrystallized from n-hexane to give ligand V-2 (yield 93%).
Example iii
Synthesis of Compound II-1.
In a flask, compound VII-1 (1 mol), 1, 8-diazabicyclo undec-7-ene DBU (2 mol) and methylene chloride (500 mL) were added, followed by stirring at room temperature for 15 hours to stop the reaction. The organic phase was washed successively with saturated NH 4 Cl, saturated brine, dried over anhydrous sodium sulfate, and then concentrated to remove the solvent, followed by separation by silica gel column chromatography (petroleum ether/ethyl acetate=2/1) to give hydroxyl group-containing γ -lactone compound II-1 (yield 93%). The characterization result is that ：1H NMR(400MHz,CDCl3):δ0.88(t,3H),1.20-1.26(m,10H),1.64(t,2H),2.06-2.35(m,4H),4.60(s,1H).
Example iv
Synthesis of Compound II-2.
In a flask, compound VII-2 (1 mol), 1, 8-diazabicyclo undec-7-ene DBU (2 mol) and methylene chloride (500 mL) were added, followed by stirring at room temperature for 13 hours to stop the reaction. The organic phase was washed successively with saturated NH 4 Cl, saturated brine, dried over anhydrous sodium sulfate, and then concentrated to remove the solvent, followed by separation by silica gel column chromatography (petroleum ether/ethyl acetate=2/1) to give hydroxyl group-containing γ -lactone compound II-2 (yield 95%).
Example v
Synthesis of Compound II-3.
In a flask, compound VII-3 (1 mol), 1, 8-diazabicyclo undec-7-ene DBU (2 mol) and methylene chloride (500 mL) were added, followed by stirring at room temperature for 13 hours to stop the reaction. The organic phase was washed successively with saturated NH 4 Cl, saturated brine, dried over anhydrous sodium sulfate, and then concentrated to remove the solvent, followed by separation by silica gel column chromatography (petroleum ether/ethyl acetate=2/1) to give hydroxyl group-containing γ -lactone compound II-3 (yield 92%).
Example 1
The compound peach aldehyde I-1 is synthesized.
Sequentially adding a raw material hydroxyl-containing gamma-lactone compound II-1 into a pressure-resistant reaction kettle at room temperature(1 Mol,1 equiv), hydrogen donor formic acid (5 mol,5 equiv), organic phosphonic acid catalyst V-1/>(0.03 Mol,3 mol%) and 300mL of methanol, the stirring speed was maintained at 800rpm. And (3) starting the programmed temperature, and after the reaction temperature is increased to 50 ℃, continuing the reaction for 3 hours, and stopping the reaction. The reaction solution was cooled to room temperature, the reaction vessel was opened, and was subjected to rotary evaporation under reduced pressure, followed by separation by silica gel column chromatography (petroleum ether/ethyl acetate=4/1) to give a peach aldehyde I-1 product in 91% yield. The characterization result is that ：1H NMR(400MHz,CDCl3):δ0.87(t,3H),1.20-1.91(m,13H),2.27-2.36(m,1H),2.50(d,1H),2.55(d,1H),4.44-4.52(m,1H).
Example 2
The compound coco aldehyde I-2 is synthesized.
Sequentially adding a raw material hydroxyl-containing gamma-lactone compound II-2 into a pressure-resistant reaction kettle at room temperature(1 Mol,1 equiv), hydrogen donor Hans ester III-1/>(1.2 Mol,1.2 equiv), the organophosphonic acid catalyst V-1 (0.03 mol,3 mol%) and toluene 300mL were kept at a stirring speed of 800rpm. And (3) starting the programmed temperature, and after the reaction temperature is raised to 60 ℃, continuing the reaction for 2.5 hours, and stopping the reaction. The reaction was cooled to room temperature, the reaction vessel was opened, and the mixture was distilled under reduced pressure and separated by silica gel column chromatography (petroleum ether/ethyl acetate=4/1) to give cocoaldehyde I-2 product in 98% yield. The characterization result is that ：1H NMR(400MHz,CDCl3):δ0.88(t,3H),1.32–1.86(m,9H),2.32–2.33(m,1H),2.52(d,1H),2.53(d,1H),4.50–4.53(m,1H).
Example 3
Synthesizing the compound delta decalactone I-3.
Sequentially adding a raw material hydroxyl-containing gamma-lactone compound II-3 into a pressure-resistant reaction kettle at room temperature(1 Mol,1 equiv), hydrogen donor Hans ester III-2/>(1.2 Mol,1.2 equiv), the organophosphonic acid catalyst V-1 (0.03 mol,3 mol%) and 300mL of dichloroethane were kept at a stirring speed of 800rpm. And (3) starting the programmed temperature, and after the reaction temperature is raised to 60 ℃, continuing the reaction for 3 hours, and stopping the reaction. The reaction was cooled to room temperature, the reaction vessel was opened, and the mixture was distilled under reduced pressure and separated by silica gel column chromatography (petroleum ether/ethyl acetate=4/1) to give the product of propiolactone I-3 in 94% yield.
Example 4
The compound peach aldehyde I-1 is synthesized.
Sequentially adding a raw material hydroxyl-containing gamma-lactone compound II-1 (1 mol,1 equiv) and a hydrogen donor hans ester III-3 into a pressure-resistant reaction kettle at room temperature(0.5 Mol,0.5 equiv) organic phosphonic acid catalyst V-2(0.1 Mol,10 mol%) and 300mL of tetrahydrofuran, the stirring speed was maintained at 800rpm. And (3) starting program cooling, and after the reaction temperature is reduced to 0 ℃, continuing to react for 72 hours, and stopping the reaction. The reaction was warmed to room temperature, the reaction vessel was opened, and the mixture was distilled under reduced pressure and separated by column chromatography on silica gel (petroleum ether/ethyl acetate=4/1) to give a peach aldehyde I-1 product in 92% yield.
Example 5
The compound coco aldehyde I-2 is synthesized.
Sequentially adding a raw material hydroxyl-containing gamma-lactone compound II-2 (1 mol,1 equiv) and a hydrogen donor hans ester III-4 into a pressure-resistant reaction kettle at room temperature(10 Mol,10 equiv), organic phosphonic acid catalyst V-2 (0.001 mol,0.1 mol%) and ethyl acetate 300mL, stirring speed was maintained at 800rpm. And (3) starting the programmed temperature, and after the reaction temperature is increased to 130 ℃, continuing the reaction for 0.5h, and stopping the reaction. The reaction was cooled to room temperature, the reaction vessel was opened, and the mixture was distilled under reduced pressure and separated by silica gel column chromatography (petroleum ether/ethyl acetate=4/1) to give cocoaldehyde I-2 product in 90% yield.
Example 6
Synthesizing the compound delta decalactone I-3.
Sequentially adding a raw material of hydroxyl-containing gamma-lactone compound II-3 (1 mol,1 equiv) and hydrogen donor isopropanol IV-1 into a pressure-resistant reaction kettle at room temperature(1 Mol,1 equiv), organic phosphonic acid catalyst V-2 (0.06 mol,6 mol%) and 300mL of tetrahydrofuran, the stirring speed was maintained at 800rpm. And (3) starting the programmed temperature, and after the reaction temperature is increased to 130 ℃, continuing the reaction for 12 hours, and stopping the reaction. The reaction was cooled to room temperature, the reaction vessel was opened, and the mixture was distilled under reduced pressure and separated by silica gel column chromatography (petroleum ether/ethyl acetate=4/1) to give the product of propiolactone I-3 in 96% yield.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.

Claims (11)

1. A method for preparing gamma-lactone compounds through hydrogenolysis reaction is characterized in that the method uses hydroxyl-containing gamma-lactone compounds as raw materials, and the hydroxyl-containing gamma-lactone compounds react with hydrogen donors under the action of an organic phosphonic acid catalyst to obtain gamma-lactone compounds;
the gamma-lactone compound is selected from the following structures:
the hydroxyl-containing gamma-lactone compound is selected from the following structures:
The organic phosphonic acid catalyst is shown in a formula V:
Wherein R 6、R7、R8、R9、R10、R11 is H, methyl, phenyl independently.
2. The method of claim 1, wherein the hydrogen donor is at least one of formic acid, a compound of formula III, a compound of formula IV:
Wherein R 2、R3 is selected from C1-C40 alkyl, C3-C12 unsubstituted cycloalkyl, C3-C12 substituted cycloalkyl, phenyl, substituted phenyl, benzyl, substituted benzyl, five-membered or six-membered heterocyclic aromatic group containing one or more oxygen, sulfur and nitrogen atoms;
R 4、R5 is selected from C1-C40 alkyl, C3-C12 unsubstituted cycloalkyl, C3-C12 substituted cycloalkyl;
wherein the substituent groups of the substituted cycloalkyl, the substituted phenyl and the substituted benzyl of the C3-C12 are selected from C1-C40 alkyl, C1-C40 alkoxy, halogen, nitro and cyano.
3. The method of any one of claims 1-2, wherein the reaction is with or without the addition of a solvent;
When the solvent is added, the solvent is at least one of methanol, ethanol, toluene, benzene, xylene, dichloromethane, dichloroethane, diethyl ether, tetrahydrofuran and ethyl acetate.
4. The process according to any one of claims 1 to 2, wherein the molar ratio of the organophosphonic acid catalyst to the hydroxyl-containing gamma-lactone compound of the starting material is (0.001-0.1): 1.
5. The process of claim 4, wherein the molar ratio of the organophosphonic acid catalyst to the hydroxyl-containing gamma-lactone compound of the starting material is from (0.01 to 0.06): 1.
6. The method according to any one of claims 1-2, wherein the molar ratio of hydrogen donor to hydroxyl-containing gamma-lactone compound of the starting material is 0.5-10:1.
7. The method of claim 6, wherein the molar ratio of the hydrogen donor to the hydroxyl-containing gamma-lactone compound of the starting material is 1-1.2:1.
8. The process according to any one of claims 1-2, wherein the reaction temperature is 0-130 ℃.
9. The process of claim 8, wherein the reaction temperature is 50-80 ℃.
10. The method according to any one of claims 1-2, wherein the reaction time is 0.5-72h.
11. The method according to claim 10, wherein the reaction time is 1-3h.
CN202310013773.2A 2023-01-05 2023-01-05 Method for preparing gamma-lactone compounds through hydrogenolysis reaction Active CN116239554B (en)

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CN114315776A (en) * 2022-01-17 2022-04-12 万华化学集团股份有限公司 Method for preparing 2, 4-disubstituted tetrahydropyrane compound through hydrogenolysis reaction
CN115417841A (en) * 2022-08-30 2022-12-02 安徽华业香料股份有限公司 High-yield synthesis method of coconut aldehyde

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CN109772457B (en) * 2019-01-28 2021-09-03 淮阴师范学院 Composite catalytic material, preparation method and application thereof in controllable preparation of dihydroxyl/dimethyl furan compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114315776A (en) * 2022-01-17 2022-04-12 万华化学集团股份有限公司 Method for preparing 2, 4-disubstituted tetrahydropyrane compound through hydrogenolysis reaction
CN115417841A (en) * 2022-08-30 2022-12-02 安徽华业香料股份有限公司 High-yield synthesis method of coconut aldehyde

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