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CN107176899A - A kind of method that oxygen oxidation alcohol or aldehyde prepares acid - Google Patents

A kind of method that oxygen oxidation alcohol or aldehyde prepares acid Download PDF

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CN107176899A
CN107176899A CN201610141434.2A CN201610141434A CN107176899A CN 107176899 A CN107176899 A CN 107176899A CN 201610141434 A CN201610141434 A CN 201610141434A CN 107176899 A CN107176899 A CN 107176899A
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oxygen
aldehyde
acid
alcohol
cdcl
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CN107176899B (en
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麻生明
姜兴国
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/88—Benzo [c] furans; Hydrogenated benzo [c] furans with one oxygen atom directly attached in position 1 or 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/08—Formation or introduction of functional groups containing oxygen of carboxyl groups or salts, halides or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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    • 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
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members 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
    • C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
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    • C07—ORGANIC CHEMISTRY
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • C07J9/005—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane containing a carboxylic function directly attached or attached by a chain containing only carbon atoms to the cyclopenta[a]hydrophenanthrene skeleton
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    • C07B2200/07—Optical isomers

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Abstract

The invention provides a method for preparing acid by oxidizing alcohol or aldehyde by using oxygen or oxygen in air as an oxidant, which is to oxidize alcohol or aldehyde by using ferric nitrate (Fe (NO) in an organic solvent at room temperature3)3·9H2O), 2,6, 6-tetramethylpiperidine oxynitride (TEMPO) and inorganic halide are used as catalysts, oxygen or air is used as an oxidant, alcohol or aldehyde is oxidized to generate acid, and glycol is oxidized to generate lactone; or aldehyde is used as a raw material, ferric nitrate is used as a catalyst, and the aldehyde oxygen reacts under a neutral conditionTo generate acid and peroxy acid. The method has the advantages of environmental protection, low cost, high yield, high atom economy, good substrate functional group compatibility, mild reaction conditions, large reaction scale and the like, and is suitable for industrial production.

Description

method for preparing acid by oxidizing alcohol or aldehyde with oxygen
Technical Field
The invention relates to a method for oxidizing alcohol or aldehyde to generate acid by taking oxygen or oxygen in air as an oxidizing agent, in particular to a method for preparing acid by oxidizing alcohol or aldehyde by oxygen or air under the catalysis of iron.
Background
Carboxylic acids are an important class of organic compounds, and have wide applications in industry, agriculture, medicine, and in people's daily life. The oxidation of alcohols to acids is a fundamental and important chemical reaction in organic chemistry. In the industrial and pharmaceutical fields, the production of carboxylic acids is often obtained by oxidative methods. Therefore, the method has good application prospect in finding a catalytic oxidation system which is efficient, low in price, mild in condition, good in functional group compatibility and environment-friendly. The difficulty in the conversion of alcohols to acids is the oxidation of aldehydes to acids. Traditionally, acid synthesis is obtained by oxidation of the corresponding alcohol using an equivalent or excess of an oxidizing agent, such as KMnO4Oxidation, Jone's oxidation and other CrO-based3The oxidation method of (2). The disadvantages of this type of process are that the oxidizing agent contains heavy metals, it is expensive, the waste liquid pollutes the environment, the reaction often requires strong acidity, the conditions are harsh, the equipment requirements are high, it is not suitable for large-scale industrial production (Oxidation of Primary Alcohols to Carboxylic Acids, Springer: Berlin, 2007; Mahmood, a.; Robinson, g.e., Powell, l.org.process res.dev.1999,3, 363-. The oxygen is an oxidant which is cheap, easy to obtain, clean, high in atom economy and environment-friendly. Air is a more ideal oxidant, does not need preparation and transportation, and is safer in industrial production. At present, the method for realizing the oxidation from alcohol to acid by using oxygen as an oxidant is very limited, and focuses on the field of noble metal catalysis, and reports of air oxidation are less frequent. As Pt catalyzed Heyns oxidation developed in 1940-s, however the expensive price and easy poisoning characteristics of Pt limit the application of Heyns oxidation to industrial production; the ginger group implemented the oxidation of benzyl alcohol to acid with dry air in 2014 with an Ag (NHC)/KOH system; davis et al reported Au/H2Catalyzing ethanol and glycerol to generate acid by an O interface; zhang Hui et al reported that a supported magnetic Pd nano catalyst catalyzes oxygen to oxidize 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid; buffin et al reported that alcohols can be oxidized by oxygen to carboxylic acids with Pd catalysisAnd a mixture of esters, benzyl alcohol can be oxidized to a mixture of aldehyde and acid; in 2015, the Li dynasty force group reported in AgO2In the/IPr system, the aldehyde is oxidized by oxygen to form an acid. Ag. There are also some reports of metal-catalyzed oxidation reactions such as Au, Ru, Pd, etc., but the substrate limitations are strong and mostly require nanotechnology or load realization (Dalmer, O.; Heyns, K.U.S. Pat.1940,2,190,377; Han, L.; Xing, P.; Jiang, B.Org.Lett.2014,16, 3428-. TEMPO provides a stable oxygen free radical which plays an important role in the concerted catalytic oxidation of alcohols with Fe or Cu to aldehydes or ketones (StahlS. S.; Ryland, B.L. Angew. chem. int.Ed.2014,53, 8824-. However, no report has been made on the oxidation of alcohols or aldehydes with oxygen to form acids in such systems.
Disclosure of Invention
The invention overcomes the defects that equivalent heavy metal is used as an oxidant or noble metal is used as a catalyst, reaction conditions are harsh, substrate functional group compatibility is poor, high temperature and high pressure are required for reaction and the like in the prior art, provides a method for generating acid by oxidizing alcohol or aldehyde by oxygen or air at room temperature and normal pressure, takes industrial easily-obtained ferric nitrate, TEMPO and inorganic halide as a co-catalyst, takes oxygen or air with wide sources as an oxidant, reduces the cost, reduces waste pollution generated in the reaction process, and has the advantages of high efficiency, mildness and easy amplification of reaction scale.
The invention aims to provide a method for preparing acid by catalyzing and oxidizing alcohol or aldehyde by oxygen, which has the advantages of mild reaction conditions, high efficiency, low cost and environmental protection.
The invention provides a method for preparing acid by oxidizing alcohol or aldehyde with oxygen, which comprises the steps of taking oxygen or oxygen in the air as an oxidizing agent, taking alcohol, glycol or aldehyde as a raw material, taking ferric nitrate, 2,6, 6-tetramethylpiperidine oxynitride (TEMPO) and inorganic halide as a catalyst, reacting for 1-48 hours under a neutral condition at room temperature in an organic solvent, oxidizing the alcohol or aldehyde to generate acid, and oxidizing the glycol to generate lactone or diacid.
In the method, the molar ratio of the alcohol, the glycol or the aldehyde, the ferric nitrate, the 2,2,6, 6-tetramethylpiperidine oxynitride and the inorganic halide is 100: 1-10: 1-20: 1-10; preferably, the molar ratio of the alcohol (or aldehyde), the ferric nitrate, the 2,2,6, 6-tetramethylpiperidine nitroxide and the inorganic halide is 100:10:20: 10.
The invention also provides a method for preparing acid by oxidizing alcohol or aldehyde with oxygen, which comprises the step of reacting aldehyde in an organic solvent at room temperature under a neutral condition by taking oxygen or oxygen in air as an oxidizing agent, taking aldehyde as a raw material and ferric nitrate as a catalyst to oxidize the aldehyde into acid and peroxy acid. According to the method, the molar ratio of the raw material aldehyde to the raw material ferric nitrate is 100-10: 1, and corresponding acid and peroxy acid are generated.
In the process of the invention, the alcohol is R1CH2OH。
Wherein R is1C1-C16 carbon chain, C3-C8 carbocycle or heterocycle, alkyl containing functional groups such as halogen, aryl, heterocycle, ester group, ether bond, alkynyl, double bond and the like, terpenes, steroids and other structures;
the halogen is fluorine, chlorine, bromine or iodine;
the aryl is phenyl, alkoxyphenyl, nitrophenyl, halophenyl, furyl or naphthyl; wherein, the alkoxy phenyl is methoxyphenyl and ethoxyphenyl, and the halogenated phenyl is fluorophenyl, chlorophenyl, bromophenyl and iodophenyl;
the heterocyclic ring is furan ring or thiophene ring.
Preferably, said R is1Carbon chain of C2-C16, carbon ring or heterocycle of C3-C8, alkyl containing functional groups such as halogen, phenyl, heterocycle, ester group, ether bond, alkynyl, double bond, etc., terpenes, steroids, etc.
Further, R1Carbon chain of C2-C16, carbon ring of C3-C8, sulfur-containing and oxygen-containing heterocyclic ring, alkyl containing functional groups such as halogen, phenyl, thienyl, furyl, ester group, ether bond, alkynyl, double bond and the like, terpenes, steroids and the like.
Still further, the raw material alcohol is octanol, dodecanol, phenylpropanol, hexadecyl alcohol, methyl 6-hydroxycaproate, 8-acetoxyoctanol, tetrahydrofuran-2-methanol, thiophene-2-ethanol, 9-bromo-1-nonanol, 2-hexyloxyethanol, 7-alkynyl-1-octanol, 4-pentyn-1-ol, 10-undecenyl-1-ol, 3-trimethylsilylpropynyl alcohol, cyclohex-3-en-1-methanol, octanediol, sclareol, (3 α,5 β) -3, 24-propanediol, or o-phthalic glycol.
In the process of the invention, the aldehyde is R2CHO。
Wherein, R is2C1-C16 carbon chain, C3-C8 carbocycle or heterocycle, and alkyl, terpenoid, steroid and other structures containing functional groups such as halogen, aryl, heterocycle, ester group, ether bond, alkynyl, double bond and the like;
wherein the halogen is fluorine, chlorine, bromine or iodine;
the aryl is phenyl, alkoxy phenyl, nitrophenyl, halogenated phenyl, thienyl, furyl or naphthyl, wherein the alkoxy phenyl is methoxyphenyl or ethoxyphenyl, and the halogenated phenyl is fluorophenyl, chlorophenyl, bromophenyl or iodophenyl;
the heterocyclic ring is furan ring or thiophene ring.
Preferably, said R is2Is C2-C16 carbon chain, C3-C8 carbocycle or heterocycle containing halogen, phenyl, heterocycle, ester group, etherBond, alkynyl, double bond and other functional groups, terpenes, steroids and other structures.
Further, said R2Carbon chain of C2-C16, carbon ring of C3-C8, sulfur-containing and oxygen-containing heterocyclic ring, alkyl containing functional groups such as halogen, phenyl, thienyl, furyl, ester group, ether bond, alkynyl, double bond and the like, terpenes, steroids and the like.
Furthermore, the raw material aldehyde is octyl aldehyde, dodecyl aldehyde, cyclohexyl formaldehyde and phenylpropyl aldehyde.
In the process of the present invention, the diols include 1, 4-diol and 1, 5-diol and 1, 8-diol.
In the method, the organic solvent is one or more of ethyl acetate, dichloromethane, 1, 2-dichloroethane, 1-dichloroethane, 1, 2-dichloropropane, 1, 3-dichloropropane, nitromethane, ethylene glycol dimethyl ether, dioxane, tetrahydrofuran, acetonitrile, benzene or toluene; preferably, the organic solvent is 1, 2-dichloroethane.
In the method, the inorganic halide is lithium halide, sodium halide, potassium halide, rubidium halide or cesium halide, and the halogen atom is fluorine, chlorine, bromine or iodine. Potassium chloride and sodium chloride are preferred. Further preferred is potassium chloride.
In the process of the present invention, when oxygen is the oxidant, the reaction time is preferably 12 hours; when oxygen in air is the oxidant, the reaction time is preferably 16 hours.
In the method, the ferric nitrate is Lewis acid, and the neutral condition means that no protonic acid or base participates, namely, no protonic acid or base is added.
Furthermore, when the oxygen in the air is used as the oxidant to amplify the reaction, two technical means can be adopted to solve the problem of amplification of the reaction in industrial production: one method is to take an air bag as a main source of oxygen, and after reacting for 1.5 hours, an oxygen ball is added as supplement; another method is to pass air slowly through the reaction vessel for oxidation purposes by a slow air flow method. The technical means avoid the danger possibly brought by the reaction under the condition of pure oxygen in industry, meet the requirements of equipment and facilitate the industrial application.
The reaction mechanism of the invention is as follows: int 1, TEMPO and Fe3+Reaction of the combined product with an alcohol to form Int 2. Int 2 elimination by β -elimination and reduction gives the aldehyde, TEMPOH, Fe2+. In the reaction system, Fe2+Can be in NO2Is reoxidized into Fe under the action of3+And NO2Is reduced to NO. NO2By NO with O2And (4) regenerating the reaction. TEMPOH passage and Fe3+Is converted back to TEMPO. Hydrate of aldehyde Int 3 by H2O in Fe3+Attack aldehyde generation under regulation of (1). The hydrate Int 3 of aldehyde undergoes a similar process to give the carboxylic acid, as shown in fig. 1.
The invention discloses a method for preparing Fe (NO) in organic solvent at room temperature3)3.9H2O, TEMPO (2,2,6, 6-tetramethylpiperidine nitroxide), and an inorganic halide (e.g., KCl) as catalysts, and oxygen or air as an oxidizing agent to oxidize alcohols or aldehydes to form the corresponding acids. The invention also discloses a method for oxidizing the aldehyde raw material into acid and peroxy acid by taking oxygen as an oxidizing agent, aldehyde as a raw material and ferric nitrate as a catalyst in an organic solvent at room temperature and reacting under a neutral condition. The method can selectively oxidize alcohol or aldehyde containing multiple functional groups such as carbon-carbon single bond, carbon-carbon double bond, carbon-carbon triple bond, halogen, ester group and the like by pure oxygen or air under normal pressure, and oxidize primary alcohol to generate corresponding acid. The method has the advantages of mild reaction conditions, high yield, simple operation, convenient separation and purification, good substrate functional group compatibility, energy conservation, greenness, environmental friendliness and the like, and is suitable for industrial production.
The invention has the advantage of wide substrate universality, can catalyze and oxidize common alcohol, can catalyze and oxidize alcohol with a more complex structure, such as alcohol containing functional groups of ester group, ether, halogen, benzene ring, heterocycle, alkynyl, double bond and the like, and even terpenes and steroid structures can be compatible under the condition of the invention, and is suitable for the field of drug research and development. The method has the advantages of high yield, mild reaction conditions, simple operation, convenient separation and purification and the like. The invention overcomes the defects that equivalent heavy metal is used as an oxidant or noble metal is used as a catalyst, the reaction conditions are harsh, the compatibility of substrate functional groups is poor, the reaction needs high temperature and high pressure and the like in the prior art. The method of the invention can be used for small-scale laboratory synthesis and is also suitable for large-scale industrial production.
The invention adopts cheap and widely available oxygen or air as an oxidant to replace the chemical oxidant used in the traditional oxidant system. The used catalysts, namely ferric nitrate, TEMPO and inorganic halide, are all industrially available reagents. The catalytic oxidation condition of the invention is very mild, so the invention can be carried out only under the conditions of room temperature, normal pressure and neutrality, and the operation is very convenient and easy to control. As the oxidant used in the reaction process is oxygen or air and the byproduct is water, the whole reaction process hardly causes any pollution to the environment and is a green chemical synthesis method. The invention has simple post-treatment and high product yield, and can effectively reduce the production and manufacturing cost.
Under the conditions of the present invention, the diol can form a lactone or a diacid. Specifically, some 1, 4-diols and 1, 5-diols may form lactones. 1, 8-diols, however, can form diacids. The method provides a new method with green, environmental protection and low cost for the synthesis of lactone and diacid products.
The invention also provides the application of the acid in laboratory preparation, drug synthesis and industrial production.
The invention also provides the application of the diacid in laboratory preparation, drug synthesis and industrial production.
The invention also provides the application of the lactone in laboratory preparation, drug synthesis and industrial production.
The invention also provides a synthetic (R) shown in the formula (I)a) -7, 8-eicosenoic acid (phlomic acid) comprising:
(1) taking 7-octyne-1-ol as a raw material, taking ferric nitrate, 2,6, 6-tetramethylpiperidine oxynitride and inorganic halide as catalysts, and carrying out oxidation reaction to obtain 7-octynoic acid;
(2) carrying out methylation reaction on the 7-octynoic acid prepared in the step (1) to obtain 7-octynoic acid methyl ester;
(3) catalyzing 7-octynoic acid methyl ester prepared in the step (2) by copper bromide and dimethyl prolinol to perform EATA reaction (asymmetric allenyl reaction of alkyne) to obtain dienoic acid methyl ester;
(4) hydrolyzing the methyl dienoate prepared in step (3) in a methanol/water system in the presence of potassium hydroxide to obtain the axial chiral dienoic acid (R) shown as formula (I)a) -7, 8-eicosenoic acid.
Wherein, the method for preparing the acid by oxidizing the alcohol or the aldehyde with the oxygen provided by the invention is adopted for preparing the 7-octynoic acid in the step (1), and the raw material is the 7-octyn-1-ol.
The reaction process is shown as a scheme (a):
in a specific experimental scheme, as shown in the reaction formula (i), dodecanol 3a is used as a raw material, and ferric nitrate (Fe (NO) is used3)3·9H2When O), 2,6, 6-tetramethyl piperidine oxynitride and KCl are used as catalysts, the content of alcohol, aldehyde and acid in the reaction is monitored by a nuclear magnetic internal standard method. Wherein, when the dosage of KCl is 10 mol%, firstly generating initial product dodecanal 1a, generating dodecanoic acid 2A after 2 hours, and completely consuming dodecanol within six hours (as shown in figure 2A); while, when 10 mol% of KCl was replaced with 10 mol% of NaCl, dodecanol could not form dodecanoic acid 2a after 4 hours (as shown in FIG. 2B).
Drawings
FIG. 1 is a schematic diagram of the reaction mechanism of the present invention.
FIG. 2A is a diagram of the production of dodecanol from a starting dodecanol with KCl as a catalyst according to the present invention; FIG. 2B shows the formation of dodecanoic acid from raw dodecanol with NaCl as catalyst according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1: synthesis of dodecanoic acid
Wherein rt is room temperature.
Under oxygen atmosphere (oxygen balloon), Fe (NO) is added3)3·9H2O (40.4mg,0.10mmol),2,2,6, 6-tetramethylpiperidine nitroxide (TEMPO, 15.5mg,0.10mmol), KCl (7.5mg,0.10mmol), dodecanol (189.0mg, 98% purity, 1.0mmol) and 1, 2-dichloroethane (DCE,4mL) were added to a 50mL Schlenk tube. Stir at rt for 12h and monitor by TLC until the reaction is complete. The reaction solution is filtered by a short column of crude silica gel, rinsed by ethyl ether (75mL) and concentrated to obtain a crude product. The crude product was chromatographed on silica gel (petroleum ether: ethyl acetate 5:1) to give the corresponding twelveAcid (199.2mg, 100%).1H NMR(400MHz,CDCl3)11.68(brs,1H,COOH),2.35(t,J＝7.6Hz,2H,CH2),1.63(quint,J＝7.3Hz,2H,CH2),1.39-1.21(m,16H,8×CH2),0.88(t,J＝7.0Hz,3H,CH3)；13C NMR(100MHz,CDCl3)180.7,34.1,31.9,29.6,29.4,29.3,29.2,29.0,24.6,22.7,14.1.
Example 2: synthesis of octanoic acid
Other operations referring to example 1, the starting material used was octanol and the reaction time was 12 hours, yielding octanoic acid (122.1mg, 85%).1H NMR(400MHz,CDCl3)11.47(brs,1H,COOH),2.35(t,J＝7.4Hz,2H,CH2),1.63(quint,J＝7.4Hz,2H,CH2),1.39-1.21(m,8H,4×CH2),0.88(t,J＝7.0Hz,3H,CH3)；13C NMR(100MHz,CDCl3)180.6,34.1,31.6,29.0,28.9,24.6,22.6,14.0.
Example 3: synthesis of phenylpropionic acid
Other workup referring to example 1, the starting material used was phenylpropanol (138.4mg, 98% purity, 1.0mmol) and the reaction time was 12 hours to give phenylpropionic acid (147.1mg, 98%).1H NMR(400MHz,CDCl3)11.48(brs,1H,COOH),7.33-7.15(m,5H,Ar-H),2.95(t,J＝8.0Hz,2H,CH2),2.67(t,J＝7.8Hz,2H,CH2)；13C NMR(100MHz,CDCl3)179.6,140.1,128.5,128.2,126.3,35.6,30.5.
Example 4: synthesis of cetyl acid
Other workup referring to example 1, the starting material used was cetyl alcohol (247.4mg, 98% purity, 1.0mmol) and the reaction time was 12 hours to give cetyl acid (254.2mg, 99%). Melting point: 62-63 ℃ (petroleum ether/ethyl acetate 100/1 recrystallisation) (literature values: 62.2-63.3 ℃);1H NMR(400MHz,CDCl3)11.60(brs,1H,COOH),2.35(t,J＝7.4Hz,2H,CH2),1.63(quint,J＝7.4Hz,2H,CH2),1.38-1.19(m,24H,12×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13C NMR(100MHz,CDCl3)180.7,34.1,31.9,29.71,29.69,29.68,29.66,29.65,29.60,29.44,29.37,29.2,29.1,24.7,22.7,14.1；IR(neat,cm-1):3300-2300,1698,1471,1430,1310,1293,1271,1250,1228,1207,1188；MS(EI)m/z(％):256(M+,60.14),73(100).
example 5: synthesis of 6-methoxy-6-carbonyl hexanoic acid
Other operations referring to example 1, the starting material used was methyl 6-hydroxycaproate (146.5mg,1.0mmol) and the reaction time was 12 hours to give 6-methoxy-6-carbonylhexanoic acid (138.4mg, 94%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1H NMR(400MHz,CDCl3)9.21(brs,1H,COOH),3.68(s,3H,CH3),2.43-2.31(m,4H,2×CH2),1.75-1.62(m,4H,2×CH2)；13C NMR(100MHz,CDCl3)179.4,173.8,51.6,33.6,24.2,24.0；IR(neat,cm-1):3400-2700,1736,1707,1438,1416,1367,1259,1199,1175,1143,1080,1016.MS(ESI,Neg)m/z(％):159(M-1)-.
Example 6: synthesis of 8-acetoxyoctanoic acid
Other workup referring to example 1, the starting material used was 8-acetoxyoctanol (187.8mg,1.0mmol) and the reaction time was 12 hours to give 8-acetoxyoctanoic acid (188.3mg, 93%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1H NMR(400MHz,CDCl3)9.58(brs,1H,COOH),4.05(t,J＝6.6Hz,2H,CH2),2.35(t,J＝7.4Hz,2H,CH2),2.05(s,3H,CH3),1.69-1.57(m,4H,2×CH2),1.42-1.30(m,6H,3×CH2)；13C NMR(100MHz,CDCl3)179.9,171.4,64.5,33.9,28.81,28.78,28.4,25.6,24.5,20.9；IR(neat,cm-1):3600-2400,1706,1464,1413,1391,1366,1234,1100,1036；MS(EI)m/z(％):202(M+,2.51),55(100).
Example 7: synthesis of tetrahydrofuran-2-carboxylic acid
Other operations referring to example 1, the starting material used was tetrahydrofuran-2-methanol (103.7mg, 99% purity, 1.0mmol) and the reaction time was 12 hours to give tetrahydrofuran-2-carboxylic acid (82.0mg, 70%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1HNMR(400MHz,CDCl3)9.82(brs,1H,COOH),4.52(dd,J1＝8.6Hz,J2＝5.4Hz,1H,CH),4.09-4.00(m,1H,one proton of CH2),3.99-3.90(m,1H,one proton of CH2),2.38-2.27(m,1H,one proton of CH2),2.16-2.06(m,1H,one proton of CH2)；2.04-1.89(m,2H,CH2)；13C NMR(100MHz,CDCl3)177.8,76.2,69.6,30.1,25.2；IR(neat,cm-1):3400-2600,1722,1449,1411,1351,1310,1203,1176,1072,1037；MS(EI)m/z(％):116(M+,1.09),71(100).
Example 8: synthesis of thiophene-2-acetic acid
Other operations reference example 1, the starting material used was thiophene-2-ethanol (130.7mg, 98% purity, 1.0mmol) and the reaction time was 12 hours to give thiophene-2-acetic acid (120.1mg, 85%) (petroleum ether: ethyl acetate ═ 5:1 to 2:1) (132.0mg,1.0mmol) and the reaction time was 2.3 hours to give thiophene-2-acetic acid (111.9mg, 86%). Melting point: 61.3-62.4 deg.C (petroleum ether/ethyl acetate recrystallization) (literature value: 61-62.5 deg.C);1H NMR(400MHz,CDCl3)10.89(brs,1H,COOH),7.24-7.20(m,1H,Ar-H),6.98-6.94(m,2H,Ar-H),3.87(s,2H,CH2)；13C NMR(100MHz,CDCl3)177.0,134.0,127.2 126.9,125.3,35.0；IR(neat,cm-1):3300-2300,1692,1438,1417,1399,1362,1331,1222,1188,1148,1128,1081,1040；MS(EI)m/z(％):142(M+,48.52),97(100).
example 9: synthesis of 9-bromo-1-nonanoic acid
Other operations referring to example 1, the starting material used was 9-bromo-1-nonanol (228.0mg, 98% purity, 1.0mmol) and the reaction time was 12 hours to give 9-bromo-1-nonanoic acid (232.6mg, 98%) (petroleum ether: ethyl acetate: 5:1 to 3: 1). Melting point: 35.3-36.5 deg.C (petroleum ether/ethyl acetate recrystallization) (literature value: 35-36.5 deg.C);1H NMR(400MHz,CDCl3)11.54(brs,1H,COOH),3.41(t,J＝6.8Hz,2H,CH2),2.36(t,J＝7.6Hz,2H,CH2),1.85(quint,J＝7.2Hz,2H,CH2),1.63(quint,J＝7.3Hz,2H,CH2),1.48-1.28(m,8H,4×CH2)；13C NMR(100MHz,CDCl3)180.4,34.0,33.9,32.7,29.0,28.8,28.5,28.0,24.5；IR(neat,cm-1):3100-2500,1689,1468,1427,1406,1338,1303,1275,1241,1211,1188,1097,1043；MS(EI)m/z(％):238(M(81Br)+,1.16),236(M(79Br)+,1.16),60(100).
example 10: synthesis of 2-hexyloxyacetic acid
Other workup referring to example 1, the starting material used was 2-hexyloxyethanol (149.8mg, 98% pure, 1.0mmol) and the reaction time was 12 hours to give 2-hexyloxyacetic acid (147.7mg, 92%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1HNMR(400MHz,CDCl3)10.14(brs,1H,COOH),4.13(s,2H,CH2),3.56(t,J＝6.8Hz,2H,CH2),1.67-1.59(m,2H,CH2),1.41-1.24(m,6H,3×CH2),0.88(t,J＝7.0Hz,3H,CH3)；13C NMR(100MHz,CDCl3)175.6,72.1,67.6,31.5,29.3,25.5,22.5,13.9.IR(neat,cm-1):3600-2500,2930,2862,1729,1462,1431,1239,1126,298,807,727,676；MS(EI)m/z(％):160(M+,2.82),83(100).
Example 11: synthesis of 7-octynoic acid
Other workup with reference to example 1, starting material 7-yne-1-octanol (126.0mg,1.0mmol) was used, reaction time was adjustedFor 12 hours, 7-octynoic acid (111.7mg, 80%) was obtained (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1H NMR(400MHz,CDCl3)11.41(brs,1H,COOH),2.38(t,J＝7.4Hz,2H,CH2),2.20(td,J1＝6.9Hz,J2＝2.5Hz,2H,≡CCH2),1.95(t,J＝2.6Hz,2H,≡CH),1.71-1.61(m,2H,CH2),1.60-1.42(m,4H,2×CH2)；13C NMR(100MHz,CDCl3)180.3,84.2,68.4,33.9,28.02,27.98,24.1,18.2.
Example 12: synthesis of 4-pentynoic acid
Other workup referring to example 1, the starting material used was 4-pentyn-1-ol (89.3mg, 95% purity, 1.0mmol) and the reaction time was 12 hours to give 4-pentynoic acid (59.3mg, 60%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1H NMR(400MHz,CDCl3)11.29(brs,1H,COOH),2.66-2.60(m,2H,CH2),2.56-2.48(m,2H,CH2),2.01(t,J＝2.8Hz,1H,≡CH)；13C NMR(100MHz,CDCl3)178.2,82.1,69.2,33.1,14.0.
Example 13: synthesis of 10-undecynoic acid
Further operation with reference to example 1, the starting material used was 10-undecen-1-ol (182.6mg,1.0mmol) and the reaction time was 12 hours to give 10-undecenoic acid (186.5mg, 95%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1H NMR(400MHz,CDCl3)11.18(brs,1H,COOH),2.35(t,J＝7.6Hz,2H,CH2),2.15-2.08(m,2H,CH2),1.78(t,J＝2.6Hz,3H,CH3),1.63(quint,J＝7.3Hz,2H,CH2),1.46(quint,J＝7.2Hz,2H,CH2),1.41-1.24(m,8H,4×CH2)；13C NMR(100MHz,CDCl3)180.5,79.3,75.3,34.1,29.1,28.98,28.95,28.91,28.8,24.6,18.7,3.4.
Example 14: synthesis of 3-trimethylsilylpropargonic acid
Other operations referring to example 1, the starting material used was 3-trimethylsilylproparganol (128.8mg,1.0mmol) and the reaction time was 36 hours to give 3-trimethylsilylpropargylic acid (93.7mg, 66%) (petroleum ether: ethyl acetate ═ 5: 1).1HNMR(400MHz,CDCl3)9.91(brs,1H,COOH),0.26(s,9H,3×CH3)；13C NMR(100MHz,CDCl3)157.6,97.4,93.8,-1.0；IR(neat,cm-1):3600-2500,2964,2176,1687,1400,1252,913,840,760；MS(EI)m/z(％):142(M+,12.82),75(100).
Example 15: synthesis of cyclohex-3-ene-1-carboxylic acid
Other operations referring to example 1, the starting material used was cyclohex-3-ene-1-methanol (114.7mg, 98% purity, 1.0mmol) and the reaction time was 48 hours to give cyclohex-3-ene-1-carboxylic acid (102.5mg, 81%) (petroleum ether: ethyl acetate ═ 5: 1).1H NMR(400MHz,CDCl3)11.01(brs,1H,COOH),5.74-5.64(m,2H,CH＝CH),2.65-2.56(m,1H,CH),2.35-2.25(m,2H,CH2),2.20-1.99(m,3H,CH2),1.78-1.65(m,1H,CH2)；13CNMR(100MHz,CDCl3)182.5,126.6,124.8,39.0,27.0,24.7,24.2.MS(EI)m/z(％):126(M+,27.78),79(100).
Example 16: synthesis of suberic acid
Other workup referring to example 1, the starting material used was octanediol (149.8mg, 98% purity, 1.0mmol) and the reaction time was 48 hours to give octanedioic acid (150.8mg, 86%) (ethyl acetate/n-hexane recrystallization). Melting point: 138.6-139.7 deg.C (literature value: 144 deg.C);1H NMR(400MHz,DMSO-d6)12.00(s,3H,CH3),2.19(t,J＝7.2Hz,4H,2×CH2),1.54-1.42(m,4H,2×CH2),1.31-1.20(m,4H,2×CH2)；13C NMR(100MHz,d6-DMSO)174.5,33.6,28.3,24.4.IR(neat,cm-1):3500-2200,1688,1466,1408,1332,1252,1190,1065,1011.MS(EI)m/z(％):174(M+,0.23),138(100).
example 17: synthesis of (+) -sclareolide
Other operations refer to example 1, the raw material used is sclareol (254.4mg,1.0mmol), the reaction time is 12 hours, and (+) -sclareolide (230.1mg, 92%) (petroleum ether: ethyl acetate: 20:1 to 5:1), melting point: 123.7-124.5 ℃ (petroleum ether/ethyl acetate recrystallization) (literature value: 121-]D 28.7＝47.9(c＝1.01,CHCl3) (literature value: [ α ]]D 20＝47(c＝1.01,CHCl3))；1H NMR(400MHz,CDCl3)2.41(dd,J1＝16.0Hz,J2＝14.8Hz,1H,one proton of CH2),2.23(dd,J1＝16.4Hz,J2＝6.4Hz,1H,CH2),2.08(dt,J1＝11.6Hz,J2＝3.2Hz,1H),1.97(dd,J1＝14.8Hz,J2＝6.6Hz,1H,CH2),1.92-1.84(m,1H,CH2),1.74-1.60(m,2H,CH2),1.50-1.31(m,7H),1.20(dt,J1＝14.0Hz,J2＝4.0Hz,1H,CH2),1.10-1.00(m,2H),0.91(s,3H,CH3),0.89(s,3H,CH3),0.84(s,3H,CH3)；13C NMR(100MHz,CDCl3)176.8,86.3,59.0,56.5,42.0,39.3,38.6,35.9,33.05,32.99,28.6,21.4,20.8,20.4,18.0,14.9；IR(neat,cm-1):2928,2897,2869,1766,1460,1390,1223,1178,1122,1017；MS(EI)m/z(％):250(M+,3.96),123(100).
Example 18: synthesis of 3-carbonyl-5 beta-cholanic acid
Other operations referring to example 1, the starting material used was (3 α,5 β) -3, 24-choladiol (362.6mg,1.0mmol) and the reaction time was 24 hours, to give 3-carbonyl-5 β -cholanic acid (272.4mg, 73%) (petroleum ether: ethyl acetate ═ 2: 1); melting point: 139.9-142.1 ℃ (petroleum ether/ethyl acetate recrystallization) (literature value: 137.7 ℃), and specific optical rotation [ α ]; α ℃)]D 25.3＝28.7(c＝1.02,CHCl3) (literature value: [ α ]]D 25.3＝28.1(c＝0.01,CHCl3))；1H NMR(400MHz,CDCl3)11.45(brs,1H,COOH),2.70(t,J＝14.2Hz,1H,CH2),2.46-2.22(m,3H),2.21-2.13(m,1H),2.08-1.98(m,3H),1.94-1.76(m,4H),1.65-1.55(m,1H),1.55-1.04(m,15H),1.02(s,3H,CH3),0.93(d,J＝6.4Hz,3H,CH3),0.69(s,3H,CH3)；13C NMR(100MHz,CDCl3)213.9,180.4,56.3,55.8,44.2,42.7,42.2,40.5,39.9,37.1,36.9,35.4,35.2,34.8,31.0,30.6,28.1,26.5,25.7,24.1,22.6,21.1,18.2,12.0.IR(neat,cm-1):3400-2500,1699,1448,1412,1380,1304,1262,1225,1182,1099.MS(EI)m/z(％):374(M+,12.22),55(100).
Example 19: synthesis of phthalide
Other workup referring to example 1, the starting material used was phthalic glycol (141.3mg, 98% purity, 1.0mmol) and the reaction time was 12 hours to give phthalide (82.7mg, 62%) (petroleum ether: ethyl acetate ═ 15:1 to 10: 1). Melting point: 72.0-73.4 deg.C (petroleum ether/ethyl acetate recrystallization) (literature value: 72-74 deg.C).1H NMR(400MHz,CDCl3)7.94(d,J＝7.6Hz,1H,Ar-H),7.70(td,J1＝7.6Hz,J2＝0.8Hz,1H,Ar-H),7.57-7.48(m,2H,Ar-H),5.34(s,2H,CH2)；13C NMR(100MHz,CDCl3)171.0,146.5,133.9,128.9,125.6,125.6,122.1,69.6；IR(neat,cm-1):2944,2924,1745,1615,1593,1466,1436,1364,1317,1286,1191,1108,1047；MS(EI)m/z(％):134(M+,46.06),105(100).
Example 20: synthesis of dodecanoic acid (air oxidation)
Fe (NO) was added to a 100mL round-bottomed flask3)3·9H2O (40.5mg,0.1mmol) and DCE (4.0mL), followed by TEMPO (15.7mg,0.1mmol), KCl (7.8mg,0.1mmol), dodecanol (189.3mg, 98% purity, 1.0mmol) and DCE (1.0 mL). The round bottom bottle is connected with the air balloon through an air extraction valve. The reaction was stirred at room temperature for 16 h until TLC monitoring completion (petroleum ether: ethyl acetate: 5: 1). The reaction mixture was filtered through a short column of crude silica gel, rinsed with ether (75mL), the solvent was spin-dried in vacuo, and purified by silica gel column chromatography (petroleum ether: ethyl acetate 5:1) to afford twelveAcid (189.7mg, 95%).1HNMR(400MHz,CDCl3)11.68(brs,1H,COOH),2.35(t,J＝7.6Hz,2H,CH2),1.63(quint,J＝7.3Hz,2H,CH2),1.39-1.21(m,16H,8×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13CNMR(100MHz,CDCl3)180.7,34.1,31.9,29.6,29.4,29.3,29.2,29.0,24.6,22.7,14.1.IR(neat,cm-1):3400-2500,1694,1466,1429,1351,1301,1278,1247,1218,1192；MS(EI)m/z(％):200(M+,21.87),73(100).
Example 21: synthesis of octanoic acid (air oxidation)
Other workup referring to example 20, the starting material used was octanol (132.0mg, 99% purity, 1.0mmol) and the reaction time was 16 hours to give octanoic acid (128.6mg, 89%) (petroleum ether: ethyl acetate ═ 5: 1).1H NMR(400MHz,CDCl3)10.26(brs,1H,COOH),2.35(t,J＝7.6Hz,2H,CH2),1.63(quint,J＝7.4Hz,2H,CH2),1.39-1.22(m,8H,4×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13C NMR(100MHz,CDCl3)180.5,34.1,31.6,29.0,28.9,24.6,22.6,14.0；IR(neat,cm-1):2925,2857,1707,1462,1413,1277,1231,1203,1109,933,725；MS(EI)m/z(％):144(M+,3.74),60(100).
Example 22: synthesis of phenylpropionic acid
Other operations with reference to example 20, the starting material used was phenylpropanol (138.6mg, 98% purity, 1.0mmol) and the reaction time was 16 hours to give phenylpropionic acid (149.0mg, 99%) (petroleum ether: ethyl acetate)Ethyl acetate 5:1 to 2: 1). Melting point: 46.6-47.6 deg.c (petroleum ether/ethyl acetate recrystallization);1H NMR(400MHz,CDCl3)10.35(brs,1H,COOH),7.33-7.16(m,5H,Ar-H),2.95(t,J＝7.8Hz,2H,CH2),2.68(t,J＝7.8Hz,2H,CH2)；13C NMR(100MHz,CDCl3)179.4,140.1,128.5,128.2,126.3,35.6,30.5；IR(neat,cm-1):3400-2400,1693,1448,1427,1300,1216,928,785,753,723,698；MS(EI)m/z(％):150(M+,38),91(100).
example 23: synthesis of cetyl acid
Other workup referring to example 20, the starting material used was cetyl alcohol (247.0mg, 98% purity, 1.0mmol) and the reaction time was 16 hours to give cetyl acid (250.5mg, 98%).1H NMR(400MHz,CDCl3)11.43(brs,1H,COOH),2.35(t,J＝7.4Hz,2H,CH2),1.63(quint,J＝7.4Hz,2H,CH2),1.36-1.21(m,24H,12×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13C NMR(100MHz,CDCl3)180.6,34.1,31.9,29.70,29.68,29.66,29.65,29.60,29.44,29.37,29.2,29.1,24.7,22.7,14.1.
Example 24: synthesis of 6-methoxy-6-carbonyl hexanoic acid
Other operations reference example 20, the starting material used was methyl 6-hydroxycaproate (146.5mg,1.0mmol) and the reaction time was 16 hours to give 6-methoxy-6-carbonylhexanoic acid (138.2mg, 86%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1H NMR(400MHz,CDCl3)9.10(brs,1H,COOH),3.68(s,3H,CH3),2.43-2.30(m,4H,2×CH2),1.75-1.62(m,4H,2×CH2)；13C NMR(100MHz,CDCl3)179.3,173.8,51.6,33.6,24.2,24.0.
Example 25: synthesis of 8-acetoxyoctanoic acid
Other workup referring to example 20, the starting material used was 8-acetoxyoctanol (187.7mg,1.0mmol) and the reaction time was 16 hours to give 8-acetoxyoctanoic acid (188.9mg, 93%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1H NMR(400MHz,CDCl3)10.62(brs,1H,COOH),4.05(t,J＝6.6Hz,2H,CH2),2.35(t,J＝7.6Hz,2H,CH2),2.05(s,3H,CH3),1.69-1.57(m,4H,2×CH2),1.42-1.30(m,6H,3×CH2)；13C NMR(100MHz,CDCl3)180.0,171.4,64.5,33.9,28.82,28.78,28.4,25.6,24.5,20.9.
Example 26: synthesis of tetrahydrofuran-2-carboxylic acid
Other operations reference example 20, the starting material used was tetrahydrofuran-2-methanol (103.0mg, 99% purity, 1.0mmol) and the reaction time was 16 hours to give tetrahydrofuran-2-carboxylic acid (85.0mg, 73%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1HNMR(400MHz,CDCl3)9.74(brs,1H,COOH),4.51(dd,J1＝8.6Hz,J2＝5.4Hz,1H,CH),4.09-4.01(m,1H,one proton of CH2),3.99-3.91(m,1H,one proton of CH2),2.38-2.27(m,1H,one proton of CH2),2.17-2.06(m,1H,one proton of CH2)；2.04-1.89(m,2H,CH2)；13C NMR(100MHz,CDCl3)177.8,76.3,69.6,30.1,25.2.
Example 27: synthesis of thiophene-2-acetic acid
Other operations reference example 20, the starting material used was thiophene-2-ethanol (130.5mg, 98% purity, 1.0mmol) and the reaction time was 16 hours to give thiophene-2-acetic acid (114.7mg, 81%) (petroleum ether: ethyl acetate ═ 5:1 to 2:1) (132.0mg,1.0 mmol).1H NMR(400MHz,CDCl3)10.90(brs,1H,COOH),7.25-7.21(m,1H,Ar-H),6.98-6.93(m,2H,Ar-H),3.87(s,2H,CH2)；13C NMR(100MHz,CDCl3)177.0,133.9,127.2126.9,125.3,35.0.
Example 28: synthesis of 9-bromo-1-nonanoic acid
Other operations reference example 20, the starting material used was 9-bromo-1-nonanol (228.0mg, 98% purity, 1.0mmol) and the reaction time was 16 hours to give 9-bromo-1-nonanoic acid (233.5mg, 98%) (petroleum ether: ethyl acetate: 5:1 to 3: 1).1HNMR(400MHz,CDCl3)11.59(brs,1H,COOH),3.41(t,J＝6.8Hz,2H,CH2),2.35(t,J＝7.4Hz,2H,CH2),1.85(quint,J＝7.2Hz,2H,CH2),1.63(quint,J＝7.3Hz,2H,CH2),1.48-1.27(m,8H,4×CH2)；13C NMR(100MHz,CDCl3)180.5,34.0,33.9,32.7,29.0,28.9,28.5,28.0,24.5.
Example 29: synthesis of 2-hexyloxyacetic acid
Other workup referring to example 20, the starting material used was 2-hexyloxyethanol (148.5mg, 98% pure, 1.0mmol) and the reaction time was 16 hours to give 2-hexyloxyacetic acid (147.7mg, 84%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1H NMR(400MHz,CDCl3)8.83(brs,1H,COOH),4.12(s,2H,CH2),3.56(t,J＝6.6Hz,2H,CH2),1.68-1.58(m,2H,CH2),1.41-1.24(m,6H,3×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13CNMR(100MHz,CDCl3)175.7,72.1,67.6,31.5,29.3,25.5,22.5,13.9.
Example 30: synthesis of 7-octynoic acid
Further operation with reference to example 20, the starting material used was 7-yne-1-octanol (126.2mg,1.0mmol) and the reaction time was 16 hours to give 7-octynoic acid (112.2mg, 80%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1).1H NMR(400MHz,CDCl3)11.01(brs,1H,COOH),2.38(t,J＝7.6Hz,2H,CH2),2.21(td,J1＝6.9Hz,J2＝2.5Hz,2H,≡CCH2),1.95(t,J＝2.6Hz,1H,≡CH),1.71-1.62(m,2H,CH2),1.61-1.42(m,4H,2×CH2)；13C NMR(100MHz,CDCl3)180.1,84.2,68.4,33.9,28.04,27.99,24.1,18.2.IR(neat)ν(cm-1)3298,2940,2864,2117,1707,1461,1413,1278,1225,1141,1085；MS(ESI,Neg)m/z(％):139(M-1)-.
Example 31: synthesis of 4-pentynoic acid
Additional workup referring to example 20, the starting material used was 4-pentyn-1-ol (89.1mg, 95% purity, 1.0mmol) and the reaction time was 16 hours to give 4-pentynoic acid (67.0mg, 68%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1). Melting point: 55.9-57.0 deg.c (petroleum ether/ethyl acetate recrystallization);1H NMR(400MHz,CDCl3)11.37(brs,1H,COOH),2.66-2.60(m,2H,CH2)，2.56-2.49(m,2H,CH2),2.01(t,J＝2.6Hz,1H,≡CH)；13C NMR(100MHz,CDCl3)178.3,82.0,69.2,33.1,14.0.IR(neat)ν(cm-1)3500-2000,3276,2927,2627,2119,1694,1426,1353,1299,1217,1024,890.MS(EI)m/z(％):98(M+,3.7),70(100)
example 32: synthesis of 10-undecynoic acid
Further operation with reference to example 20, the starting material used was 10-undecen-1-ol (182.8mg,1.0mmol) and the reaction time was 16 hours to give 10-undecenoic acid (176.2mg, 90%) (petroleum ether: ethyl acetate ═ 5:1 to 2: 1). Melting point: 51.3-52.2 deg.c (petroleum ether/ethyl acetate recrystallization);1H NMR(400MHz,CDCl3)9.57(brs,1H,COOH),2.35(t,J＝7.6Hz,2H,CH2),2.15-2.08(m,2H,CH2),1.78(t,J＝2.6Hz,3H,CH3),1.63(quint,J＝7.3Hz,2H,CH2),1.46(quint,J＝7.1Hz,2H,CH2),1.41-1.24(m,8H,4×CH2)；13C NMR(100MHz,CDCl3)180.4,79.3,75.3,34.1,29.1,28.98,28.96,28.91,28.8,24.6,18.7,3.4.IR(neat)ν(cm-1)3500-2400,1693,1464,1434,1410,1347,1321,1293,1260,1226,1193.MS(EI)m/z(％):196(M+,0.57),68(100).
example 33: synthesis of 3-trimethylsilylpropargonic acid
Other operations referring to example 20, the starting material used was 3-trimethylsilylproparganol (128.6mg,1.0mmol) and the reaction time was 48 hours to give 3-trimethylsilylpropargylic acid (92.9mg, 65%) (petroleum ether: ethyl acetate ═ 5: 1).1HNMR(400MHz,CDCl3)6.78(brs,1H,COOH),0.26(s,9H,3×CH3)；13C NMR(100MHz,CDCl3)157.4,97.4,93.7,-1.0.
Example 34: synthesis of cyclohex-3-ene-1-carboxylic acid
Further operation with reference to example 20, the starting material used was cyclohex-3-ene-1-methanol (115.9mg, 98% purity, 1.0mmol) and the reaction time was 48 hours to give cyclohex-3-ene-1-carboxylic acid (89.9mg, 70%) (petroleum ether: ethyl acetate ═ 5: 1).1H NMR(400MHz,CDCl3)11.63(brs,1H,COOH),5.75-5.60(m,2H,CH2),2.68-2.55(m,1H,CH),2.36-2.00(m,5H,CH2),1.78-1.65(m,1H,CH2)；13C NMR(100MHz,CDCl3)182.7,126.7,124.9,39.1,27.1,24.8,24.3.
Example 35: synthesis of suberic acid
Other operationsReferring to example 20, the starting material used was octanediol (148.8mg, 98% purity, 1.0mmol) and the reaction time was 48 hours to give octanedioic acid (144.4mg, 83%) (ethyl acetate/n-hexane recrystallization).1H NMR(400MHz,DMSO-d6)12.00(s,3H,CH3),2.19(t,J＝7.4Hz,4H,2×CH2),1.54-1.41(m,4H,2×CH2),1.31-1.21(m,4H,2×CH2)；13C NMR(100MHz,d6-DMSO)174.5,33.6,28.3,24.4.
Example 35: synthesis of (+) -sclareolide
Other operations referring to example 20, the raw material used was sclareol (254.8mg,1.0mmol) and the reaction time was 16 hours, yielding (+) -sclareolide (233.5mg, 93%) (petroleum ether: ethyl acetate: 20:1 to 5: 1.) chiral [ α ]]D 28.7＝46.9(c＝1.00,CHCl3) (literature value: [ α ]]D 20＝47(c＝1.01,CHCl3))；1H NMR(400MHz,CDCl3)2.41(dd,J1＝15.6Hz,J2＝15.6Hz,1H,CH2),2.23(dd,J1＝15.0Hz,J2＝6.4Hz,1H,CH2),2.08(dt,J1＝11.6Hz,J2＝3.3Hz,1H),1.97(dd,J1＝14.8Hz,J2＝6.6Hz,1H,CH2),1.92-1.84(m,1H,CH2),1.74-1.63(m,2H,CH2),1.50-1.31(m,7H),1.20(dt,J1＝13.5Hz,J2＝4.3Hz,1H,CH2),1.10-1.00(m,2H),0.91(s,3H,CH3),0.89(s,3H,CH3),0.84(s,3H,CH3)；13C NMR(100MHz,CDCl3)176.7,86.2,59.0,56.5,42.0,39.4,38.6,35.9,33.05,32.99,28.6,21.5,20.8,20.4,18.0,14.9.
Example 36: synthesis of phthalide
Other workup referring to example 20, the starting material used was phthalic glycol (141.3mg, 98% purity, 1.0mmol) and the reaction time was 16 hours to give phthalide (88.3mg, 66%) (petroleum ether: ethyl acetate ═ 15:1 to 10: 1).1H NMR(400MHz,CDCl3)7.92(d,J＝7.6Hz,1H,Ar-H),7.70(td,J1＝7.6Hz,J2＝1.2Hz,1H,Ar-H),7.58-7.49(m,2H,Ar-H),5.34(s,2H,CH2)；13C NMR(100MHz,CDCl3)171.1,146.5,134.0,129.0,125.62,125.57,122.1,69.6.
Example 37: synthesis of 7-octynoic acid
Fe (NO) was added to a Schlenk tube in sequence under an oxygen atmosphere (oxygen balloon)3)3·9H2O (202.8mg,0.5mmol), TEMPO (78.3mg,4.0mmol), NaCl (29.3mg,0.5mmol), 7-octyn-1-ol (631.4mg,5.0mmol) and 1, 2-dichloroethane (DCE,20.0mL), the reaction stirred at room temperature for 20 hours, monitored by TLC (petroleum ether: ethyl acetate ═ 5:1) until the reaction was complete, the reaction mixture filtered through a crude silica gel short column, rinsed with diethyl ether (3 × 40mL), the solvent was spin dried in vacuo, and silica gel column chromatography (petroleum ether: ethyl acetate ═ 5:1 to 2:1) afforded product 7-octynoic acid (599.1mg, 85%).1HNMR(400MHz,CDCl3)11.29(brs,1H,COOH),2.38(t,J＝7.6Hz,2H,CH2),2.20(td,J1＝7.0Hz,J2＝2.8Hz,2H,C≡CCH2),1.95(t,J＝2.8Hz,1H,C≡CH),1.71-1.61(m,2H,CH2),1.60-1.41(m,4H,2×CH2)；13C NMR(100MHz,CDCl3)180.3,84.2,68.4,33.9,28.02,27.99,24.1,18.2.
Example 38: synthesis of hexadecyl acid (oxygen)
Under oxygen atmosphere (oxygen balloon), Fe (NO) was added to a 500mL three-necked flask in sequence3)3·9H2O (1.6164g,4.0mmol), TEMPO (625.3mg,4.0mmol), KCl (298.4mg,4.0mmol) and DCE (4.0mL) then cetyl alcohol (9.8191g, 98% pure, 40.0mmol) was added, the reaction stirred at room temperature for 16 hours, monitored by TLC (petroleum ether: ethyl acetate 5:1) until completion, the reaction mixture filtered through a short column of crude silica gel, rinsed with diethyl ether (4 × 120mL), after vacuum spin drying of the solvent, the crude product was purified by recrystallization (first petroleum ether: ethyl acetate 10:1 recrystallized to 8.5404g, after spin drying of the filtrate, petroleum ether: ethyl acetate 18:1 recrystallized to 1.1413 g) to afford hexadecyl acid (9.6817g, 94%).1HNMR(400MHz,DMSO-d6)11.99(brs,1H,COOH),2.18(t,J＝7.4Hz,2H,CH2),1.53-1.42(m,2H,CH2),1.32-1.16(m,24H,12×CH2),0.85(t,J＝6.6Hz,3H,CH3)；13C NMR(100MHz,CDCl3)180.8,34.1,31.9,29.69,29.67,29.66,29.59,29.43,29.37,29.2,29.0,24.6,22.7,14.1.
Example 39: synthesis of cetyl acid (air + oxygen)
Adding Fe (NO) into a 1L three-mouth bottle in sequence3)3·9H2O (1.6162g,4.0mmol), DCE (120mL), TEMPO (625.3mg,4.0mmol), KCl (298.6mg,4.0mmol) and cetyl alcohol (9.8968g, 98% purity, 40.0 mmol). The three-necked flask was then connected to a 70L air bag via an air extraction valve. Stirring at room temperature for 1.5h, and evacuating at the other portThe reaction was stirred at room temperature and monitored by TLC (petroleum ether: ethyl acetate 5:1) until the reaction was complete over 21.5 hours, the reaction mixture was filtered through a short column of crude silica gel, rinsed with ether (4 × 120mL), the solvent was dried in vacuo and the crude product was recrystallized (petroleum ether: ethyl acetate 15:1) to afford the hexadecyl acid (9.0540g, 88%).1H NMR(400MHz,DMSO-d6)11.99(brs,1H,COOH),2.18(t,J＝7.4Hz,2H,CH2),1.52-1.43(m,2H,CH2),1.30-1.19(m,24H,12×CH2),0.85(t,J＝6.8Hz,3H,CH3)；13CNMR(100MHz,CDCl3)180.6,34.1,31.9,29.70,29.69,29.67,29.66,29.65,29.59,29.44,29.37,29.24,29.1,24.7,22.7,14.1.
Example 40: synthesis of cetyl acid (Slow air flow)
Sequentially adding Fe (NO) into a 2L three-mouth bottle3)3·9H2O (9.6952g,24.0mmol), TEMPO (3.7514g,24.0mmol), KCl (1.7885g,24.0mmol) and 1, 2-dichloroethane (DCE,400mL), after stirring at room temperature for 10 minutes, cetyl alcohol (59.3883g, 98% pure, 40.0mmol) and DCE (100mL) were added, a three-necked flask was passed through a bleed valve with a slow air stream, the reaction was stirred at room temperature, monitored by TLC (petroleum ether: ethyl acetate ═ 5:1) until completion after 24 hours, the reaction mixture was filtered through a short column of crude silica gel, rinsed with ether (3 × 500mL), the solvent was vacuum dried and the crude product was recrystallized (petroleum ether: ethyl acetate ═ 20:1) to give hexadecyl acid (55.0232g, 89%).1H NMR(400MHz,DMSO-d6)11.99(brs,1H,COOH),2.18(t,J＝7.4Hz,2H,CH2),1.52-1.43(m,2H,CH2),1.31-1.18(m,24H,12×CH2),0.85(t,J＝6.6Hz,3H,CH3)；13C NMR(100MHz,CDCl3)180.5,34.1,31.9,29.67,29.65,29.64,29.62,29.57,29.42,29.35,29.2,29.0,24.7,22.7,14.1.
Example 41: synthesis of dodecanoic acid
Under oxygen atmosphere (oxygen balloon), Fe (NO) is added3)3·9H2O (40.4mg,0.10mmol),2,2,6, 6-tetramethylpiperidine nitroxide (TEMPO, 15.5mg,0.10mmol), KCl (7.5mg,0.10mmol), dodecanal (184.3mg,1.0mmol) and 1, 2-dichloroethane (DCE,4mL) were added to a Schlenk tube. Stir at rt for 12h and monitor by TLC until the reaction is complete. The reaction mixture was filtered through a short column of crude silica gel, rinsed with diethyl ether (75mL) and concentrated to give the crude product. The crude product was chromatographed on silica gel (petroleum ether: ethyl acetate 5:1) to give the corresponding dodecanoic acid (187.9mg, 94%). Melting point: 43-44 deg.C (petroleum ether/ethyl acetate recrystallization) (literature value: 43-44 deg.C);1H NMR(400MHz,CDCl3)＝11.56(brs,1H,COOH),2.35(t,J＝7.4Hz,2H,CH2),1.63(quint,J＝7.1Hz,2H,CH2),1.40-1.18(m,16H,8×CH2),0.88(t,J＝6.6Hz,3H,CH3)；13C NMR(100MHz,CDCl3)180.6,34.1,31.9,29.6,29.4,29.3,29.2,29.0,24.7,22.7,14.1；MS(EI)m/z(％):200(M+,20.99),73(100)；IR(neat):v＝2954,2916,2871,2848,1697,1470,1429,1411,1351,1328,1302,1277,1248,1220,1193,1084cm-1.
example 42: synthesis of Cyclohexanecarboxylic acid
Other operations referring to example 41, the starting material used was cyclohexanal, and the reaction time was 12 hours, to give cyclohexanecarboxylic acid (115.4mg, 90%) (petroleum ether: ethyl acetate ═ 5: 1).1H NMR(400MHz,CDCl3)＝11.43(brs,1H,COOH),2.33(tt,J＝11.2,3.6Hz,1H,Ha),2.00-1.88(m,2H,Hb),1.84-1.70(m,2H,He),1.70-1.58(m,1H,Hf),1.55-1.38(m,2H,Hc),1.37-1.18(m,3H,Hdand Hg)；13C NMR(100MHz,CDCl3)＝182.9,42.9,28.7,25.6,25.3；MS(EI)m/z(％):128(M+,53.29),55(100)；IR(neat):v＝2930,2855,1698,1451,1417,1311,1295,1256,1212,1182,1136,1021cm-1.
Example 43: synthesis of octanoic acid
Other operations referring to example 41, the starting material used was octanal (128.1mg) and the reaction time was 12 hours to give octanoic acid (138.4mg, 96%) (petroleum ether: ethyl acetate ═ 5: 1).1H NMR(400MHz,CDCl3)11.33(brs,1H,COOH),2.35(t,J＝7.4Hz,2H,CH2),1.63(quint,J＝7.3Hz,2H,CH2),1.38-1.22(m,8H,4×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13C NMR(100MHz,CDCl3)＝180.6,34.1,31.6,29.0,28.9,24.6,22.6,14.0；MS(EI)m/z(％):144(M+,2.09),60(100)；IR(neat,cm-1)＝2956,2925,2857,1706,1459,1412,1379,1275,1230,1203,1108cm-1.
Example 44: synthesis of phenylpropionic acid
Other operations with reference to example 41, the starting material was phenylpropanal (141.3mg, 98% purity, 1.0mmol) and the reaction time was 12 hours to give phenylpropionic acid (144.9mg, 9)6%) (petroleum ether: ethyl acetate 5:1 to 2: 1).1H NMR(400MHz,CDCl3)11.56(brs,1H,COOH),7.32-7.25(m,2H,Ar-H),7.23-7.16(m,2H,Ar-H),2.95(t,J＝7.8Hz,2H,CH2),2.67(t,J＝7.8Hz,2H,CH2)；13C NMR(100MHz,CDCl3)179.6,140.1,128.5,128.2,126.3,35.6,30.5；MS(EI)m/z(％):150(M+,50.1),91(100)；IR(neat,cm-1)3030-2620,1693,1602,1497,1448,1427,1407,1358,1300,1216,1158,1082cm-1.
Example 45: synthesis of dodecanoic acid
Fe (NO) was added to a 100mL round-bottomed flask3)3·9H2O (40.5mg,0.1mmol) and DCE (4.0mL), followed by TEMPO (15.6mg,0.1mmol), KCl (7.5mg,0.1mmol), dodecanal (183.8mg,1.0mmol) and DCE (1.0 mL). The round bottom bottle is connected with the air balloon through an air extraction valve. The reaction was stirred at room temperature for 16 h until TLC monitoring completion (petroleum ether: ethyl acetate: 5: 1). The reaction mixture was filtered through a short column of crude silica gel, rinsed with ether (75mL), the solvent was spin-dried in vacuo and purified by silica gel column chromatography (petroleum ether: ethyl acetate 5:1) to give dodecanoic acid (176.5mg, 88%).1H NMR(400MHz,CDCl3)11.49(brs,1H,COOH),2.35(t,J＝7.6Hz,2H,CH2),1.63(quint,J＝7.3Hz,2H,CH2),1.40-1.18(m,16H,8×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13C NMR(100MHz,CDCl3)＝180.5,34.1,31.9,29.6,29.4,29.3,29.2,29.0,24.6,22.7,14.1.
Example 46: synthesis of Cyclohexanecarboxylic acid
Other operations referring to example 45, the starting material used was cyclohexylformaldehyde (112.7mg,1.0mmol) and the reaction time was 16 hours to give cyclohexanecarboxylic acid (106.4mg, 83%) (petroleum ether: ethyl acetate ═ 5: 1).1H NMR(400MHz,CDCl3)＝11.42(brs,1H,COOH),2.33(tt,J＝11.2,3.6Hz,1H,Ha),2.00-1.88(m,2H,Hb),1.84-1.70(m,2H,He),1.70-1.60(m,1H,Hf),1.55-1.38(m,2H,Hc),1.37-1.18(m,3H,Hdand Hg)；13CNMR(100MHz,CDCl3)＝182.9,42.9,28.7,25.6,25.3.
Example 47: synthesis of octanoic acid
Other workup referring to example 45, octanal (128.7mg,1.0mmol) was used as the starting material and the reaction time was 16 hours to give octanoic acid (139.7mg, 97%) (petroleum ether: ethyl acetate ═ 5: 1).1H NMR(400MHz,CDCl3)＝11.02(brs,1H,COOH),2.35(t,J＝7.6Hz,2H,CH2),1.63(quint,J＝7.4Hz,2H,CH2),1.38-1.18(m,8H,4×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13C NMR(100MHz,CDCl3)＝180.6,34.1,31.6,29.0,28.9,24.6,22.6,14.0.
Example 48: synthesis of phenylpropionic acid
Other operations with reference to example 45, the starting material used was phenylpropanal (141.5mg, 98% purity, 1.0mmol) and the reaction time was 16 hours to give phenylpropionic acid (147.7mg, 98%) (petroleum ether: ethyl acetate)Ethyl acetate 5:1 to 2: 1).1H NMR(400MHz,CDCl3)11.09(brs,1H,COOH),7.32-7.25(m,2H,Ar-H),7.24-7.17(m,2H,Ar-H),2.95(t,J＝7.8Hz,2H,CH2),2.67(t,J＝7.8Hz,2H,CH2)；13C NMR(100MHz,CDCl3)179.5,140.1,128.5,128.2,126.3,35.6,30.5.
Example 49: synthesis of (Ra) -7, 8-eicosenoic acid (natural product phlomic acid)
Reference example 30 was synthesized from 7-octynoic acid.
Synthesis of methyl 7-octynoate
To a round bottom flask were added the substrates 7-octynoic acid (981.7mg,7.0mmol) and Et2O/MeOH mixed solvent (4/1,35 mL). The system is cooled to 0 ℃, and TMSCHN is added dropwise2(2.0M,5.25mL), the mixture was allowed to return to room temperature and stirred. TLC showed the reaction was complete after 2 hours. The solvent was spun off. Purification by silica gel column chromatography (petroleum ether/diethyl ether: 30/1) afforded methyl 7-octynoate (898.3mg, 83%):1H NMR(400MHz,CDCl3)3.67(s,3H,OMe),2.33(t,J＝7.4Hz,2H,CH2),2.20(td,J1＝6.9Hz,J2＝2.5Hz,2H,≡CCH2),1.95(t,J＝2.6Hz,1H,≡CH),1.70-1.60(m,2H,CH2),1.60-1.50(m,2H,CH2),1.49-1.39(m,2H,CH2)；13C NMR(100MHz,CDCl3)174.0,84.2,68.3,51.4,33.8,28.1,28.0,24.3,18.1；IR(neat)ν(cm-1)3296,2943,2863,2117,1738,1460,1436,1364,1325,1263,1205,1174,1145,1087,1071,1008.MS(ESI)m/z(％):155.1(M+1)-.
(Ra) -synthesis of methyl 7, 8-eicosanoate:
sequentially adding CuBr into the dried sealed tube under argon atmosphere2(134.1mg,0.6mmol), (S) -dimethylprolinol (3)87.2mg,3.0mmol), methyl 7-octynoate (694.2mg,4.5mmol)/dioxane (4.5mL) and dodecanal (830.1mg,4.5mmol)/dioxane (4.5mL), the tube was stoppered with Teflon and placed in a preheated oil bath at 130 ℃ for 12 hours with stirring. TLC plates were monitored (petroleum ether/diethyl ether 5/1). The resulting mixture was used in 90mL Et2Diluted with O, washed with 60mL of 3M HCl solution, separated, and the aqueous phase was treated with 30 × 3mL Et 3mL2And (4) extracting. The organic phases are combined, washed with saturated NaCl solution and anhydrous NaSO4And (5) drying. Filtering, spin-drying, and separating by silica gel column chromatography (petroleum ether/diethyl ether: 100/1) to obtain (R)a) -methyl 7, 8-eicosanoate (565.2mg, 58%). 95% ee (HPLC conditions: Chiralcel PA-H column, hexane/i-PrOH. RTM. 100/0,1.0mL/min, λ. RTM. 214nm, tR(major)＝17.2min,tR(minor)＝22.1min)；[α]D 30.6＝-36.8(c＝1.015,CHCl3)；1H NMR(400MHz,CDCl3)5.11-5.00(m,2H,CH＝C＝CH),3.66(s,3H,CH3),2.30(t,J＝7.6Hz,2H,CH2),2.02-1.93(m,4H,2×CH2),1.63(quint,J＝7.5Hz,2H,CH2),1.46-1.20(m,22H,11×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13CNMR(100MHz,CDCl3)203.8,174.2,91.1,90.5,51.4,34.0,31.9,29.65,29.63,29.62,29.5,29.3,29.2,29.1,29.0,28.73,28.71,28.6,24.8,22.7,14.1；IR(neat)ν(cm-1)2923,2853,1962,1742,1462,1437,1362,1255,1199,1170,1087,1012；MS(EI)m/z(％)322(M+,6.73),150(100)；HRMS calcd.for C21H38O2(M+):322.2872；Found:322.2876.
Product (R)a) -synthesis of 7, 8-eicosenoic acid (phlomic acid):
KOH (141.0mg,2.5mmol), mixed solvent (5mL, MeOH/H) was added to the flask in sequence2O-4/1), and (R)a) -methyl 7, 8-eicosanoate (322.0mg,1 mmol)/solvent mixture (5mL, MeOH/H)2O-4/1). The system was stirred at 60 ℃ and monitored by TLC, after 2h the reaction was complete. The system was placed in an ice bath and 3M HCl (ca.1mL) was added dropwise. MeOH was removed by rotation and 30mL CH was added2Cl2And 25mL of water. Is divided into liquid components ofThe organic phase is separated and the aqueous phase is treated with CH2Cl2Extraction (15mL × 3), organic phases are combined, washed with saturated NaCl solution, dried with anhydrous NaSO4, filtered, dried and separated by silica gel column chromatography (petroleum ether/diethyl ether 10/1 to 2/1) to yield the natural product, phlomic acid (283.6mg, 92%).1H NMR(400MHz,CDCl3)11.7(brs,1H,COOH),5.11-5.01(m,2H,CH＝C＝CH),2.35(t,J＝7.6Hz,2H,CH2),2.02-1.93(m,4H,2×CH2),1.65(quint,J＝7.5Hz,2H,CH2),1.49-1.20(m,22H,11×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13CNMR(100MHz,CDCl3)203.8,180.5,91.1,90.5,34.1,31.9,29.67,29.66,29.64,29.5,29.4,29.2,29.1,29.0,28.71,28.69,28.5,24.5,22.7,14.1；IR(neat)ν(cm-1)2915,2849,1964,1708,1683,1458,1415,1331,1285,1246,1200.MS(EI)m/z(％):308(M+,5.91),168(100)；HRMS calcd.for C20H36O2(M+):308.2715；Found:308.2717.
Methyl esterification derived assay product (R)a) Ee value of 7, 8-eicosenoic acid (phlomic acid):
to a round bottom flask was added the natural product phlomic acid (55.9mg,0.2mmol) and the mixed solvent (5mL, Et)2O/MeOH 4/1). After the temperature of the system is reduced to 0 ℃,0.2 mL of TMSCHN is added dropwise2(2M in hexane,0.4 mmol). The ice bath was removed and the reaction mixture was allowed to return to room temperature. The reaction was monitored by TLC and after 2.5h the reaction was complete. Removing the solvent by rotation, and separating by silica gel column chromatography (petroleum ether/diethyl ether-100/1) to obtain liquid (R)a) -methyl 7, 8-eicosanoate (63.1mg, 97%). 96% ee (HPLCconditions: Chiralcel PA-H column, hexane/i-PrOH. RTM. 100/0,1.0mL/min, λ. RTM. 214nm, tR(major)＝23.7min,tR(minor)＝32.3min)；[α]D 30.5＝-39.9(c＝0.99,CHCl3)；1H NMR(400MHz,CDCl3)5.11-5.01(m,2H,CH＝C＝CH),3.67(s,3H,CH3),2.36(t,J＝7.6Hz,2H,CH2),2.03-1.92(m,4H,2×CH2),1.63(quint,J＝7.5Hz,2H,CH2),1.46-1.20(m,22H,11×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13C NMR(100MHz,CDCl3)203.8,174.2,91.1,90.6,51.4,34.0,31.9,29.66,29.63,29.5,29.3,29.2,29.1,29.0,28.73,28.71,28.6,24.8,22.7,14.1.
Example 50 Synthesis of dodecanoic acid (dodecaperoxy acid)
Under oxygen atmosphere (oxygen balloon), Fe (NO) is added3)3·9H2O (40.7mg,0.10mmol), dodecanal (184.2mg,1.0mmol) and 1, 2-dichloroethane (DCE,4mL) were added to a Schlenk tube. Stir at rt for 12h and monitor by TLC until the reaction is complete. The reaction mixture was filtered through a short column of crude silica gel, rinsed with diethyl ether (75mL) and concentrated to give the crude product. Adding 35 μ L dibromomethane as internal standard, and performing nuclear magnetic quantitative hydrogen spectrum (1H NMR) yield of 78% of lauric acid and 11% of lauric peroxyacid. The crude product was chromatographed on silica gel (petroleum ether: ethyl acetate 20:1 to 5:1) to give dodecanoic acid and dodecaperoxy acid. Dodecanoic acid:1H NMR(400MHz,CDCl3)11.49(brs,1H,COOH),2.35(t,J＝7.6Hz,2H,CH2),1.63(quint,J＝7.2Hz,2H,CH2),1.38-1.21(m,16H,8×CH2),0.88(t,J＝6.6Hz,3H,CH3)；13CNMR(100MHz,CDCl3) 180.6,34.1,31.9,29.6,29.4,29.3,29.2,29.0,24.6,22.7,14.1 dodecaperoxyacid:1HNMR(400MHz,CDCl3)11.38(brs,1H,CO3H),2.42(t,J＝7.6Hz,2H,CH2),1.70(quint,J＝7.3Hz,2H,CH2),1.39-1.19(m,16H,8×CH2),0.88(t,J＝6.8Hz,3H,CH3)；13CNMR(100MHz,CDCl3)＝174.7,31.9,30.4,29.54,29.51,29.32,29.29,29.0,28.9,24.6,22.7,14.1.

Claims (14)

1. A method for oxidizing alcohol or aldehyde by oxygen is characterized in that at room temperature, in an organic solvent, oxygen is used as an oxidizing agent, alcohol, diol or aldehyde is used as a raw material, ferric nitrate, 2,6, 6-tetramethylpiperidine oxynitride and inorganic halide are used as catalysts, the reaction is carried out under neutral conditions, the alcohol or aldehyde is oxidized to generate acid, and the diol is oxidized to generate lactone or diacid; wherein,
the starting alcohol is R1CH2OH；R1Comprises a carbon chain of C1-C16, a carbocyclic or heterocyclic ring of C3-C8, and a fluorine-, chlorine-, bromine-, iodine-, aryl-, hetero-ringThe structure of ring, ester group, ether bond, alkynyl, alkyl, terpenoid and steroid of double bond functional group;
the raw material diols include 1, 4-diol, 1, 5-diol and 1, 8-diol;
the starting aldehyde is R2CHO；R2Comprises C1-C16 carbon chain, C3-C8 carbocycle or heterocycle, and alkyl, terpenoid and steroid structure containing fluorine, chlorine, bromine, iodine, aryl, heterocycle, ester group, ether bond, alkynyl and double bond functional group.
2. A method for oxidizing alcohol or aldehyde by oxygen is characterized in that at room temperature, in an organic solvent, oxygen is used as an oxidizing agent, aldehyde is used as a raw material, ferric nitrate is used as a catalyst, and the aldehyde is oxidized to generate acid and peroxy acid under a neutral condition;
wherein the starting aldehyde is R2CHO；R2Comprises C1-C16 carbon chain, C3-C8 carbocycle or heterocycle, and alkyl, terpenoid and steroid structure containing fluorine, chlorine, bromine, iodine, aryl, heterocycle, ester group, ether bond, alkynyl and double bond functional group.
3. The method for the oxygen oxidation of an alcohol or aldehyde according to claim 1 or 2, wherein the aryl group is a phenyl group, an alkoxyphenyl group, a nitrophenyl group, a halophenyl group, a thienyl group, a furyl group, or a naphthyl group; the alkoxy phenyl is methoxyphenyl and ethoxyphenyl, and the halogenated phenyl is fluorophenyl, chlorophenyl, bromophenyl and iodophenyl;
the heterocyclic ring is furan ring or thiophene ring.
4. The method for oxidizing alcohol or aldehyde with oxygen according to claim 2, wherein the molar ratio of the raw material aldehyde to the raw material ferric nitrate is 100 to 10: 1.
5. The method for oxidizing alcohol or aldehyde with oxygen according to claim 1, wherein the molar ratio of the raw material, ferric nitrate, 2,6, 6-tetramethylpiperidine nitroxide, and inorganic halide is 100:1 to 10:1 to 20:1 to 10.
6. The method for oxidizing an alcohol or aldehyde with oxygen according to claim 5, wherein the molar ratio of the raw material, ferric nitrate, 2,6, 6-tetramethylpiperidine nitroxide, inorganic halide is 100:10:20: 10.
7. The method for the oxygen oxidation of an alcohol or aldehyde according to claim 1, wherein the inorganic halide is a lithium halide, a sodium halide, a potassium halide, a rubidium halide, a cesium halide, and the halogen atom is fluorine, chlorine, bromine, or iodine.
8. The method for the oxygen oxidation of an alcohol or aldehyde according to claim 7, wherein the inorganic halide is potassium chloride or sodium chloride.
9. The method for oxygen oxidizing an alcohol or aldehyde according to claim 1, wherein the reaction time is 1 to 48 hours.
10. The method for oxidizing an alcohol or aldehyde with oxygen according to claim 1, wherein the oxygen is pure oxygen or oxygen in air.
11. The method for oxygen oxidizing an alcohol or aldehyde according to claim 1, wherein the neutral condition is that no protic acid or base is added.
12. The method for the oxygen oxidation of an alcohol or aldehyde according to claim 1, wherein the organic solvent is one or more selected from the group consisting of ethyl acetate, dichloromethane, 1, 2-dichloroethane, 1-dichloroethane, 1, 2-dichloropropane, 1, 3-dichloropropane, nitromethane, ethylene glycol dimethyl ether, dioxane, tetrahydrofuran, acetonitrile, benzene, and toluene.
13. The method for oxidizing an alcohol or aldehyde with oxygen according to claim 1 or 2, wherein the oxygen may be oxygen in air;
wherein, the method adopted when introducing air is to take an air bag as a main source of oxygen, and an oxygen ball is added as supplement after reacting for 1.5 hours; or by a slow air flow method, allowing air to flow slowly through the reaction vessel.
14. Synthesis of (R)a) A method of producing (R) -7, 8-eicosenoic acid, wherein said (R) isa) The structure of the-7, 8-eicosenoic acid is shown in the formula (I), and the method comprises the following steps:
(1) taking 7-octyne-1-ol as a raw material, taking ferric nitrate, 2,6, 6-tetramethylpiperidine oxynitride and inorganic halide as catalysts, and carrying out oxidation reaction to obtain 7-octynoic acid;
(2) carrying out methylation reaction on the 7-octynoic acid prepared in the step (1) to obtain 7-octynoic acid methyl ester;
(3) catalyzing the 7-octynoic acid methyl ester prepared in the step (2) by copper bromide and dimethyl prolinol to perform EATA reaction to obtain dienoic acid methyl ester;
(4) hydrolyzing the methyl dienoate prepared in step (3) in a methanol/water system in the presence of potassium hydroxide to obtain the axial chiral dienoic acid (R)a) -7, 8-eicosenoic acid;
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