CN107176899A - The method that a kind of dioxygen oxidation alcohol or aldehyde prepare acid - Google Patents

The method that a kind of dioxygen oxidation alcohol or aldehyde prepare 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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aldehyde
acid
alcohol
oxygen
nmr
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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
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    • 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
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    • C07—ORGANIC CHEMISTRY
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    • 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
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    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
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    • 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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    • C07—ORGANIC CHEMISTRY
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    • C07B2200/07—Optical isomers

Abstract

The present invention provides a kind of method that oxygen using in oxygen or air prepares acid as oxidizing alcohol or aldehyde, ties up at room temperature, in organic solvent, with ferric nitrate (Fe (NO3)3·9H2O), 2,2,6,6 tetramethyl piperidine nitrogen oxides (TEMPO) and inorganic halides are catalyst, using oxygen or air as oxidant, by alcohol or oxidation of aldehydes generation acid, glycol oxidation generation lactone；Or, using aldehyde as raw material, using ferric nitrate as catalyst, react in neutral conditions, oxidation of aldehydes the generation acid and peroxy acid.The present invention has the advantages that environmental protection, cost are low, yield is high, Atom economy is high, the compatible good, reaction condition of substrate functional group is gentle, reaction scale can amplify, and is suitably applied industrial production.

Description

The method that a kind of dioxygen oxidation alcohol or aldehyde prepare acid
Technical field
The present invention relates to a kind of oxygen using in oxygen or air as oxidizing alcohol or the sour method of aldehyde production, specifically Be related to it is a kind of be catalyzed with iron, pass through the method that oxygen or air oxidation alcohol or aldehyde prepare acid.
Background technology
Carboxylic acid is an important class organic compound, is had extensively in industry, agricultural, medicine and daily life Using.A kind of oxidation reaction from alcohol to acid basic, important chemical reaction in being organic chemistry.In industry and pharmacy neck Domain, the method for the production normal open peroxidating of carboxylic acid is obtained.Therefore, a kind of efficient, cheap, mild condition, functional group are found Good, the environment-friendly catalytic oxidation system of compatibility has a good application prospect.The difficult point converted from alcohol to acid is from aldehyde To the oxidation of acid.Traditionally, it is sour to be synthesized by aoxidizing corresponding alcohol using equivalent or the oxidant of excess and obtaining, such as KMnO4Oxidation, Jone ' s are aoxidized and other are based on CrO3Method for oxidation etc..The shortcoming of such method is that oxidant contains heavy metal, Expensive, waste liquor contamination environment, reaction often needs highly acid, and condition is harsh, high to equipment requirement, is not suitable for extensive work Industry produces (Oxidation of Primary Alcohols to Carboxylic Acids, Springer:Berlin, 2007；Mahmood,A.；Robinson,G.E.；Powell,L.Org.Process Res.Dev.1999,3,363-364； Thottathil,J.K.；Moniot,J.L.；Mueller,R.H.；Wong,M.K.Y.；Kissick, T.P.J.Org.Chem.1986,51,3140-3143).Oxygen is a kind of cheap and easy to get, cleaning, high atom economy, environment friend Good oxidant.Air is more preferably oxidant, safer in the industrial production without preparing and transporting.At present, with Oxygen is that oxidant realizes very limited to the method for oxidation of acid from alcohol, and concentrates on precious metal catalyst field, air oxidation Report is more rare.The Heyns oxidations of Pt catalysis develop such as the 1940- ages, however expensive Pt price be easy to what is poisoned Feature limits Heyns and aoxidizes the application in industrial production；Jiang Biao groups were realized in 2014 with Ag (NHC)/KOH systems Acid is generated using dry air oxidation Bian alcohol；Davis et al. reports Au/H2O interface catalysis ethanol and glycerine generation acid； Zhang Zehui et al. reports the magnetic Pd nanocatalyst oxygen catalytic oxidations 5 hydroxymethyl furfural generation 2,5- furans two of load Formic acid；Buffin et al. is reported under Pd catalysis, and alcohol can be oxidized by oxygen the mixture for carboxylic acid and ester, and Bian alcohol can be oxidized to The mixture of aldehyde and acid；2015, group of Li Chao armies was reported in AgO2In/IPr systems, acid is generated by dioxygen oxidation aldehyde.Ag、 The oxidation reaction of the metal catalytics such as Au, Ru, Pd also has certain report, but substrate limitation is strong, nanometer technology is needed mostly or negative Carry and realize (Dalmer, O.；Heyns,K.U.S.Pat.1940,2,190,377；Han,L.；Xing,P.；Jiang, B.Org.Lett.2014,16,3428-3431；Zope,B.N.；Hibbitts,D.D.；Neurock,M.；Davis, R.J.Science,2010,330,74-78；Kerdi,F.；Rass,H.A.；Pinel,C.；Besson,M.；Peru,G.； Leger,B.；Rio,S.；Monflier,E.；Ponchel,A.Appl.Catal.A.2015,506,206-219；Buffin, B.P.；Clarkson,J.P.；Belitz,N.L.；Kundu,A.J.Mol.Catal.A.2005,225,111-116；eLiu, M.X.；Wang,H.N.；Zeng,H.Y.；Li,C.J.Sci.Adv.2015,1,e1500020).TEMPO can provide a kind of stable Oxygen radical, with Fe or Cu concerted catalysis oxidation alcohol obtain aldehydes or ketones during played an important role (Stahl S.S.；Ryland,B.L.Angew.Chem.Int.Ed.2014,53,8824-8838；Cao,Q.；Dornan,L.M.；Rogan, L.；Hughes,N.L.；Muldoon,M.J.Chem.Commun.,2014,50,4524-4543).But in such system also not The report of dioxygen oxidation alcohol or aldehyde generation acid can be realized.
The content of the invention
Instant invention overcomes be oxidant or noble metal is catalyst, reaction condition using equivalent heavy metal in the prior art Comparing harsh, substrate functional group poor compatibility, reaction needs the defects such as HTHP there is provided one kind by under room temperature normal pressure, by Oxygen or air oxidation alcohol or aldehyde are come the method for generating acid, and the ferric nitrate being easy to get using industry, TEMPO, inorganic halides are as altogether Catalyst, using originate extensive oxygen or air as oxidant, reduces cost, reduces the waste produced in course of reaction Pollution, is easy to the advantage of amplification with efficient, gentle, reaction scale.
It is an object of the invention to provide a kind of reaction condition it is gentle, efficiently, low cost, environmental protection catalytic oxygen oxygen Change the method that alcohol or aldehyde prepare acid.
A kind of method that the dioxygen oxidation alcohol or aldehyde that the present invention is provided prepare acid, at room temperature, in organic solvent, with oxygen Oxygen in gas or air is as oxidant, using alcohol, glycol or aldehyde as raw material, with ferric nitrate, 2,2,6,6- tetramethyl piperidine nitrogens Oxide (TEMPO), inorganic halides are as catalyst, and the reaction time is 1-48 hours, alcohol or oxidation of aldehydes in neutral conditions Generation acid, glycol oxidation generation lactone or diacid.
In the inventive method, the alcohol, glycol or aldehyde, ferric nitrate, 2,2,6,6- tetramethyl piperidine nitrogen oxides, inorganic halide The mol ratio of compound is 100:1~10:1~20:1~10；Preferably, the alcohol (or aldehyde), ferric nitrate, 2,2,6,6- tetramethyls Piperidines nitrogen oxides, the mol ratio of inorganic halides are 100:10:20:10.
Sour method is prepared present invention also offers a kind of dioxygen oxidation alcohol or aldehyde, at room temperature, in organic solvent, with Oxygen in oxygen or air, using aldehyde as raw material, using ferric nitrate as catalyst, reacts in neutral conditions as oxidant, Oxidation of aldehydes generation acid and peroxy acid.In the inventive method, the raw material aldehyde, ferric nitrate mol ratio are 100~10:1, generation is corresponding Acid and peroxy acid.
In the inventive method, the alcohol is R1CH2OH。
Wherein, R1Refer to C1-C16 carbochain, C3-C8 carbocyclic ring or heterocycle contain halogen, aryl, heterocycle, ester group, ether The alkyl of the functional groups such as key, alkynyl, double bond, the structure such as terpene, steroidal；
The halogen is fluorine, chlorine, bromine, iodine；
The aryl is phenyl, alkoxyl phenyl, nitrobenzophenone, halogenophenyl, furyl or naphthyl；Wherein, the alkane Phenyl is methoxyphenyl, ethoxyl phenenyl, and the halogenophenyl is difluorophenyl, chlorophenyl, bromo phenyl, iodo Phenyl；
The heterocycle is furan nucleus, thiphene ring.
Preferably, the R1For C2-C16 carbochain, C3-C8 carbocyclic ring or heterocycle contain halogen, phenyl, heterocycle, ester The alkyl of the functional groups such as base, ehter bond, alkynyl, double bond, the structure such as terpene, steroidal.
Further, R1For C2-C16 carbochain, C3-C8 carbocyclic ring, sulfur-bearing, oxygen alicyclic heterocyclic contain halogen, phenyl, thiophene The alkyl of the functional groups such as fen base, furyl, ester group, ehter bond, alkynyl, double bond, the structure such as terpene, steroidal.
Further, the raw alcohol be octanol, lauryl alcohol, phenylpropanol, cetyl alcohol, 6 hydroxycaproic acid methyl esters, 8- acetoxyl groups octanol, tetrahydrofuran-2-methanol, Thiophene-2-Ethanol, the bromo- 1 nonyl alcohols of 9-, 2- hexyloxyethanols, 7- alkynes -1- are pungent Alcohol, 4- pentyne-1-alcohols, 10- undecyne -1- alcohol, 3- trimethyl silicon substrates propilolic alcohol, hexamethylene -3- alkene -1- methanol, ethohexadiol, fragrant purple Soviet Union's glycol, (3 α, 5 β) -3,24- courages glycol, adjacent Benzenediol.
In the inventive method, the aldehyde is R2CHO。
Wherein, the R2Refer to C1-C16 carbochain, C3-C8 carbocyclic ring or heterocycle contain halogen, aryl, heterocycle, ester The structures such as alkyl, terpene, the steroidal of the functional groups such as base, ehter bond, alkynyl, double bond；
Wherein, the halogen is fluorine, chlorine, bromine, iodine；
The aryl be phenyl, alkoxyl phenyl, nitrobenzophenone, halogenophenyl, thienyl, furyl or naphthyl, wherein, The alkoxyl phenyl is methoxyphenyl, ethoxyl phenenyl, and the halogenophenyl is difluorophenyl, chlorophenyl, bromobenzene Base, iodine substituted phenyl；
The heterocycle is furan nucleus, thiphene ring.
Preferably, the R2For C2-C16 carbochain, C3-C8 carbocyclic ring or heterocycle contain halogen, phenyl, heterocycle, ester The alkyl of the functional groups such as base, ehter bond, alkynyl, double bond, the structure such as terpene, steroidal.
Further, the R2For C2-C16 carbochain, C3-C8 carbocyclic ring, sulfur-bearing, oxygen alicyclic heterocyclic contain halogen, benzene The alkyl of the functional groups such as base, thienyl, furyl, ester group, ehter bond, alkynyl, double bond, the structure such as terpene, steroidal.
Further, the raw material aldehyde is octanal, lauric aldehyde, hexahydrobenzaldehyde, benzenpropanal.
In the inventive method, the glycol includes Isosorbide-5-Nitrae-glycol and 1,5- glycol and 1,8- glycol.
In the inventive method, the organic solvent is ethyl acetate, dichloromethane, 1,2- dichloroethanes, the chloroethenes of 1,1- bis- Alkane, 1,2- dichloropropanes, 1,3- dichloropropanes, nitromethane, glycol dimethyl ether, dioxane, tetrahydrofuran, acetonitrile, benzene Or one or more mixing in toluene；Preferably, the organic solvent is 1,2- dichloroethanes.
In the inventive method, the inorganic halides are lithium halide, sodium halide, potassium halide, rubidium halide, caesium halide, and halogen is former Son is fluorine, chlorine, bromine, iodine.Preferably potassium chloride, sodium chloride.More preferably potassium chloride.
In the inventive method, when oxygen is oxidant, the reaction time is preferably 12 hours；When the oxygen in air When gas is oxidant, the reaction time is preferably 16 hours.
In the inventive method, ferric nitrate is lewis acid, and the neutrallty condition refers to that no Bronsted acid or alkali are participated in, i.e., do not add Protonation acid or alkali.
Further, can also be using two kinds of technologies when reaction is amplified by oxidant of the oxygen in air in the present invention Means, the problem of solving to react amplification in industrial production：A kind of method is the main source using air bag as oxygen, reaction After 1.5 hours, increase oxygen ball is used as supplement；Another method is, by slow air stream method, air is slowly flowed across instead Container is answered, oxidation purpose is realized.These technological means react the danger that may be brought under the conditions of avoiding industrial purity oxygen, full Sufficient equipment requirement, is easy to industrial application.
The present invention reaction mechanism be：Int 1, TEMPO and Fe3+With reference to product, with alcohol reaction generation Int 2.Int 2 Aldehyde, TEMPOH, Fe have been obtained by β-elimination and reduction elimination2+.In reaction system, Fe2+Can be in NO2Under effect again It is oxidized to Fe3+, and NO2It is reduced to NO.NO2Pass through NO and O2Reaction regeneration.TEMPOH by and Fe3+Reaction turned Change returns to TEMPO.The hydrate Int 3 of aldehyde passes through H2O is in Fe3+Regulation under attack aldehyde generate.The hydrate Int 3 of aldehyde undergoes One similar process obtains carboxylic acid, as shown in Figure 1.
The invention discloses at room temperature, in organic solvent, with Fe (NO3)3.9H2O, TEMPO (2,2,6,6- tetramethyls Piperidines nitrogen oxides) and inorganic halides (such as KCl) be catalyst, oxidant, oxidation alcohol or aldehyde life are used as using oxygen or air Into corresponding sour method.The invention also discloses at room temperature, in organic solvent, using oxygen as oxidant, using aldehyde as Raw material, using ferric nitrate as catalyst, reacts in neutral conditions, the method for the oxidation of aldehydes generation acid of raw material and peroxy acid.This hair Bright method, by purity oxygen under normal pressure or air, can will contain carbon-carbon single bond, carbon-carbon double bond, triple carbon-carbon bonds, halogen, ester group etc. The alcohol or aldehyde of a variety of functional groups are optionally aoxidized, by the corresponding acid of primary alcohol oxidation generation.The present invention has reaction condition temperature With, yield is high, simple to operate, isolate and purify conveniently, it is good substrate functional group compatibility, energy-conservation, green, environment-friendly etc. many excellent Point, is a method which be suitable for industrial production.
The present invention has the advantages that substrate universality is wide, both can the common alcohol of catalysis oxidation, again available for catalysis oxidation structure More complicated alcohol, such as containing ester group, ether, halogen, phenyl ring, heterocycle, alkynyl, alcohol of double bond functional group etc., or even terpene, steroid Body structure also can be compatible under the conditions of the present invention, it is adaptable to Field of Drug Discovery.The present invention has yield height, reaction condition temperature With, it is simple to operate, isolate and purify the advantages of facilitating.Instant invention overcomes in the prior art using equivalent heavy metal be oxidant or Noble metal be catalyst, harsher reaction condition, substrate functional group poor compatibility, reaction need the defects such as HTHP.This hair Bright method, can be not only used for small-scale laboratory's synthesis, is also applied for large-scale industrial production.
The present invention, as oxidant, substitutes institute in conventional oxidation agent system using the cheap, oxygen of wide material sources or air The chemical oxidizing agent used.Used catalyst ferric nitrate, TEMPO and inorganic halides are that industry is easy to get reagent.Due to this hair Bright catalysis oxidation condition is extremely gentle, therefore, need to only can be carried out under conditions of room temperature, normal pressure, neutrality, operation is extremely just It is sharp and easily controllable.Because oxidant used is oxygen or air in course of reaction, accessory substance is water, therefore, is entirely reacted Journey does not almost result in any pollution to environment, is a kind of green chemical synthesis method.Present invention post processing is simple, product yield Height, can effectively reduce manufacturing cost.
Under the conditions of the present invention, glycol can generate lactone or diacid.Specifically, part Isosorbide-5-Nitrae-glycol and 1,5- glycol can Generate lactone.And 1,8- glycol can generate diacid.This be lactone and two acid products synthesis also provide a kind of environmental protection, into This low new method.
The invention also provides application of the acid in laboratory preparation, pharmaceutical synthesis, industrial production.
The invention also provides application of the diacid in laboratory preparation, pharmaceutical synthesis, industrial production.
The invention also provides the lactone, the application in laboratory preparation, pharmaceutical synthesis, industrial production.
The invention also provides (R shown in one kind synthesis formula (I)a) -7,8- 20 olefin(e) acid (phlomic acid) side Method, methods described includes：
(1) using 7- octyne -1- alcohol as raw material, with ferric nitrate, 2,2,6,6- tetramethyl piperidine nitrogen oxides, inorganic halides For catalyst, occur oxidation reaction and obtain 7- octynic acids；
(2) methylation reaction is carried out to 7- octynic acids prepared by step (1), obtains 7- methyl 2-octynoates；
(3) the 7- methyl 2-octynoates prepared by copper bromide, dimethyl dried meat ammonia alcohol catalysis step (2), occur EATA reactions (the asymmetric alkenyl reaction of alkynes), obtains joining e pioic acid methyl ester；
(4) in the presence of potassium hydroxide, in methanol/water system, connection e pioic acid methyl ester prepared by hydrolysing step (3) is obtained The connection olefin(e) acid of axial chirality shown in formula (I) (Ra) 20 olefin(e) acids of -7,8-.
Wherein, the step (1) prepares 7- octynic acids and uses dioxygen oxidation alcohol proposed by the present invention or aldehyde preparation The method of acid, the raw material is 7- octyne -1- alcohol.
Shown in the course of reaction such as route (a)：
In a specific experimental program, such as shown in reaction equation (i), using lauryl alcohol 3a as raw material, with ferric nitrate (Fe (NO3)3·9H2O it is anti-with the monitoring of nuclear-magnetism internal standard method when), 2,2,6,6- tetramethyl piperidine nitrogen oxides and KCl are as catalyst Should middle alcohol, aldehyde, the content of acid.Wherein, when KCl consumption is 10mol%, initial product lauric aldehyde 1a is firstly generated, after 2 hours Lauric acid/dodecanoic acid 2a is generated, lauryl alcohol was consumed complete (as shown in Figure 2 A) in six hours；And substitute 10mol% with 10mol%NaCl KCl when, lauryl alcohol can not still generate lauric acid/dodecanoic acid 2a (as shown in Figure 2 B) at 4 hours.
Brief description of the drawings
Fig. 1 is the schematic diagram of reaction mechanism of the present invention.
In Fig. 2 Fig. 2A for the present invention using KCl as catalyst when by raw material lauryl alcohol generate product lauric acid/dodecanoic acid；Fig. 2 B are this Product lauric acid/dodecanoic acid is generated by raw material lauryl alcohol when invention is using NaCl as catalyst.
Embodiment
With reference to specific examples below and accompanying drawing, the present invention is described in further detail.The process of the implementation present invention, Condition, experimental method etc., are the universal knowledege and common knowledge of this area, this hair in addition to the following content specially referred to It is bright that content is not particularly limited.
Embodiment 1：The synthesis of lauric acid/dodecanoic acid
Wherein, rt is room temperature.
Under oxygen atmosphere (oxygen ball), by Fe (NO3)3·9H2O (40.4mg, 0.10mmol), 2,2,6,6- tetramethyls Piperidines nitrogen oxides (TEMPO, 15.5mg, 0.10mmol), KCl (7.5mg, 0.10mmol), (189.0mg, 98% is pure for lauryl alcohol Degree, 1.0mmol) and 1,2- dichloroethanes (DCE, 4mL) be added in 50mL Schlenk pipes.12h, TLC monitorings is stirred at room temperature Until reaction is completed.The thick short column of silica gel filtering of reaction solution, ether (75mL) elution is concentrated to give crude product.The crude product passes through silicon Plastic column chromatography (petroleum ether：Ethyl acetate=5:1) corresponding lauric acid/dodecanoic acid (199.2mg, 100%) is obtained.1H NMR(400MHz, CDCl3) δ 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)δ180.7, 34.1,31.9,29.6,29.4,29.3,29.2,29.0,24.6,22.7,14.1.
Embodiment 2：The synthesis of octanoic acid
Other operation reference implementation examples 1, raw materials used is octanol, and the reaction time is 12 hours, obtain octanoic acid (122.1mg, 85%).1H NMR(400MHz,CDCl3) δ 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)δ180.6,34.1,31.6,29.0,28.9,24.6,22.6,14.0.
Embodiment 3：The synthesis of benzenpropanoic acid
Other operation reference implementation examples 1, raw materials used is phenylpropanol (138.4mg, 98% purity, 1.0mmol), during reaction Between be 12 hours, obtain benzenpropanoic acid (147.1mg, 98%).1H NMR(400MHz,CDCl3)δ11.48(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)δ179.6,140.1,128.5,128.2,126.3,35.6,30.5.
Embodiment 4：The synthesis of cetyl acid
Other operation reference implementation examples 1, raw materials used is cetyl alcohol (247.4mg, 98% purity, 1.0mmol), instead It is 12 hours between seasonable, obtains cetyl sour (254.2mg, 99%).Fusing point：62-63 DEG C (petrol ether/ethyl acetate= 100/1 recrystallization) (literature value:62.2–63.3℃)；1H NMR(400MHz,CDCl3)δ11.60(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)δ180.7,34.1,31.9,29.71,29.69,29.68, 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).
Embodiment 5：The synthesis of 6- methoxyl group -6- carbonyl caproic acids
Other operation reference implementation examples 1, raw materials used is 6 hydroxycaproic acid methyl esters (146.5mg, 1.0mmol), during reaction Between be 12 hours, obtain 6- methoxyl group -6- carbonyls caproic acid (138.4mg, 94%) (petroleum ether:Ethyl acetate=5:1 to 2:1).1H NMR(400MHz,CDCl3)δ9.21(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)δ179.4,173.8,51.6,33.6,24.2,24.0； 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)-.
Embodiment 6：The synthesis of 8- acetoxyl groups octanoic acid
Other operation reference implementation examples 1, raw materials used is 8- acetoxyl groups octanol (187.8mg, 1.0mmol), during reaction Between be 12 hours, obtain sad (188.3mg, the 93%) (petroleum ether of 8- acetoxyl groups:Ethyl acetate=5:1 to 2:1).1H NMR (400MHz,CDCl3) δ 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)δ179.9,171.4,64.5,33.9,28.81,28.78,28.4,25.6,24.5,20.9；IR(neat, cm-1):3600-2400,1706,1464,1413,1391,1366,1234,1100,1036；MS (EI) m/z (%):202(M+, 2.51),55(100).
Embodiment 7：The synthesis of tetrahydrofuran -2- formic acid
Other operation reference implementation examples 1, it is raw materials used for tetrahydrofuran-2-methanol (103.7mg, 99% purity, 1.0mmol), the reaction time is 12 hours, obtains tetrahydrofuran -2- formic acid (82.0mg, 70%) (petroleum ether:Ethyl acetate= 5:1 to 2:1).1HNMR(400MHz,CDCl3)δ9.82(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)δ177.8,76.2,69.6,30.1,25.2；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).
Embodiment 8：The synthesis of thiophene -2- acetic acid
Other operation reference implementation examples 1, raw materials used is Thiophene-2-Ethanol (130.7mg, 98% purity, 1.0mmol), Reaction time is 12 hours, obtains thiophene -2- acetic acid (120.1mg, 85%) (petroleum ether:Ethyl acetate=5:1 to 2:1) (132.0mg, 1.0mmol), the reaction time is 2.3 hours, obtains thiophene -2- acetic acid (111.9mg, 86%).Fusing point：61.3- 62.4 DEG C of (petrol ether/ethyl acetate recrystallization) (literature values:61-62.5℃)；1H NMR(400MHz,CDCl3)δ10.89 (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)δ177.0,134.0,127.2 126.9,125.3,35.0；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).
Embodiment 9：The synthesis of the bromo- 1- n-nonanoic acids of 9-
Other operation reference implementation examples 1, raw materials used is the bromo- 1 nonyl alcohols of 9- (228.0mg, 98% purity, 1.0mmol), Reaction time is 12 hours, obtains the bromo- 1- n-nonanoic acids of 9- (232.6mg, 98%) (petroleum ether:Ethyl acetate=5:1 to 3:1).It is molten Point：35.3-36.5 DEG C (petrol ether/ethyl acetate recrystallization) (literature value:35-36.5℃)；1H NMR(400MHz,CDCl3)δ 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)δ180.4,34.0,33.9,32.7,29.0,28.8,28.5,28.0,24.5；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).
Embodiment 10：The synthesis of 2- hexyloxy acetic acid
Other operation reference implementation examples 1, raw materials used is 2- hexyloxyethanols (149.8mg, 98% purity, 1.0mmol), Reaction time is 12 hours, obtains 2- hexyloxies acetic acid (147.7mg, 92%) (petroleum ether:Ethyl acetate=5:1 to 2:1).1H NMR(400MHz,CDCl3)δ10.14(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)δ175.6,72.1,67.6,31.5,29.3,25.5,22.5,13.9.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).
Embodiment 11：The synthesis of 7- octynic acids
Other operation reference implementation examples 1, raw materials used is 7- alkynes -1- octanols (126.0mg, 1.0mmol), and the reaction time is 12 hours, obtain 7- octynic acids (111.7mg, 80%) (petroleum ether:Ethyl acetate=5:1 to 2:1).1H NMR(400MHz, CDCl3) δ 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)δ180.3,84.2,68.4,33.9,28.02,27.98,24.1,18.2.
Embodiment 12：The synthesis of 4- pentinoic acids
Other operation reference implementation examples 1, raw materials used is 4- pentyne-1-alcohols (89.3mg, 95% purity, 1.0mmol), instead It is 12 hours between seasonable, obtains 4- pentinoic acids (59.3mg, 60%) (petroleum ether:Ethyl acetate=5:1 to 2:1).1H NMR (400MHz,CDCl3)δ11.29(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)δ178.2,82.1,69.2,33.1,14.0.
Embodiment 13：The synthesis of 10- undecynes acid
Other operation reference implementation examples 1, raw materials used is 10- undecyne -1- alcohol (182.6mg, 1.0mmol), during reaction Between be 12 hours, obtain sour (186.5mg, the 95%) (petroleum ether of 10- undecynes:Ethyl acetate=5:1 to 2:1).1H NMR (400MHz,CDCl3) δ 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)δ180.5,79.3,75.3,34.1,29.1, 28.98,28.95,28.91,28.8,24.6,18.7,3.4.
Embodiment 14：The synthesis of 3- trimethyl silicon substrate propiolic acids
Other operation reference implementation examples 1, raw materials used is 3- trimethyl silicon substrate propilolic alcohols (128.8mg, 1.0mmol), instead It is 36 hours between seasonable, obtains 3- trimethyl silicon substrates propiolic acid (93.7mg, 66%) (petroleum ether:Ethyl acetate=5:1).1H NMR(400MHz,CDCl3)δ9.91(brs,1H,COOH),0.26(s,9H,3×CH3)；13C NMR(100MHz,CDCl3)δ 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).
Embodiment 15：The synthesis of hexamethylene -3- alkene -1- formic acid
Other operation reference implementation examples 1, it is raw materials used for hexamethylene -3- alkene -1- methanol (114.7mg, 98% purity, 1.0mmol), the reaction time is 48 hours, obtains hexamethylene -3- alkene -1- formic acid (102.5mg, 81%) (petroleum ether:Ethyl acetate =5:1).1H NMR(400MHz,CDCl3) δ 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)；13C NMR(100MHz,CDCl3) δ 182.5,126.6,124.8,39.0,27.0,24.7,24.2.MS (EI) m/z (%):126(M+, 27.78),79(100).
Embodiment 16：The synthesis of suberic acid
Other operation reference implementation examples 1, raw materials used is ethohexadiol (149.8mg, 98% purity, 1.0mmol), during reaction Between be 48 hours, obtain suberic acid (150.8mg, 86%) (ethyl acetate/n-hexane recrystallization).Fusing point：138.6-139.7℃ (literature value:144℃)；1H NMR(400MHz,DMSO-d6)δ12.00(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)δ 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).
Embodiment 17：The synthesis of (+)-Clary sage lactone
Other operation reference implementation examples 1, raw materials used for fragrant purple perilla glycol (254.4mg, 1.0mmol), the reaction time is 12 hours, obtain (+)-Clary sage lactone (230.1mg, 92%) (petroleum ether:Ethyl acetate=20:1 to 5:1).Fusing point： 123.7-124.5 DEG C (petrol ether/ethyl acetate recrystallization) (literature value：121-124℃)；Specific rotation [α]D 28.7=47.9 (c= 1.01,CHCl3) (literature value:[α]D 20=47 (c=1.01, CHCl3))；1H NMR(400MHz,CDCl3)δ2.41(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)δ176.8,86.3,59.0,56.5,42.0,39.3,38.6,35.9,33.05,32.99,28.6, 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).
Embodiment 18：The synthesis of -5 β of 3- carbonyls-cholanic acid
Other operation reference implementation examples 1, raw materials used is (3 α, 5 β) -3,24- courages glycol (362.6mg, 1.0mmol), instead It is 24 hours between seasonable, obtains -5 β of 3- carbonyls-cholanic acid (272.4mg, 73%) (petroleum ether:Ethyl acetate=2:1).Fusing point： 139.9-142.1 DEG C (petrol ether/ethyl acetate recrystallization) (literature value：137.7℃)；Specific rotation [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)δ11.45 (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)δ213.9,180.4,56.3, 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).
Embodiment 19：The synthesis of phthalide
Other operation reference implementation examples 1, it is raw materials used for adjacent Benzenediol (141.3mg, 98% purity, 1.0mmol), reaction Time is 12 hours, obtains phthalide (82.7mg, 62%) (petroleum ether:Ethyl acetate=15:1 to 10:1).Fusing point：72.0- 73.4 DEG C of (petrol ether/ethyl acetate recrystallization) (literature values：72-74℃).1H NMR(400MHz,CDCl3) δ 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)δ171.0,146.5,133.9,128.9,125.6,125.6,122.1, 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).
Embodiment 20：The synthesis (air oxidation) of lauric acid/dodecanoic acid
Fe (NO are added in 100mL round-bottomed bottles3)3·9H2O (40.5mg, 0.1mmol) and DCE (4.0mL), is subsequently added into TEMPO (15.7mg, 0.1mmol), KCl (7.8mg, 0.1mmol), lauryl alcohol (189.3mg, 98% purity, 1.0mmol) and DCE(1.0mL).Round-bottomed bottle is connected by extraction valve with air balloon.Reaction is stirred at room temperature 16 hours, until TLC monitorings Reaction completes (petroleum ether:Ethyl acetate=5:1).Reactant mixture is filtered by thick short column of silica gel, and ether (75mL) elution is true Sky is spin-dried for after solvent, silica gel column chromatography (petroleum ether:Ethyl acetate=5:1) purifying obtains lauric acid/dodecanoic acid (189.7mg, 95%).1H NMR(400MHz,CDCl3) δ 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)δ180.7,34.1,31.9,29.6,29.4,29.3,29.2,29.0,24.6,22.7,14.1.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).
Embodiment 21：The synthesis (air oxidation) of octanoic acid
Other operation reference implementation examples 20, raw materials used is octanol (132.0mg, 99% purity, 1.0mmol), during reaction Between be 16 hours, obtain sad (128.6mg, 89%) (petroleum ether:Ethyl acetate=5:1).1H NMR(400MHz,CDCl3)δ 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)δ180.5,34.1, 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).
Embodiment 22：The synthesis of benzenpropanoic acid
Other operation reference implementation examples 20, raw materials used is phenylpropanol (138.6mg, 98% purity, 1.0mmol), reaction Time is 16 hours, obtains benzenpropanoic acid (149.0mg, 99%) (petroleum ether:Ethyl acetate=5:1 to 2:1).Fusing point：46.6- 47.6 DEG C (petrol ether/ethyl acetate recrystallization)；1H NMR(400MHz,CDCl3)δ10.35(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)δ179.4,140.1,128.5,128.2,126.3,35.6,30.5；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).
Embodiment 23：The synthesis of cetyl acid
Other operation reference implementation examples 20, raw materials used is cetyl alcohol (247.0mg, 98% purity, 1.0mmol), Reaction time is 16 hours, obtains cetyl sour (250.5mg, 98%).1H NMR(400MHz,CDCl3)δ11.43(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)δ180.6,34.1,31.9,29.70, 29.68,29.66,29.65,29.60,29.44,29.37,29.2,29.1,24.7,22.7,14.1.
Embodiment 24：The synthesis of 6- methoxyl group -6- carbonyl caproic acids
Other operation reference implementation examples 20, raw materials used is 6 hydroxycaproic acid methyl esters (146.5mg, 1.0mmol), during reaction Between be 16 hours, obtain 6- methoxyl group -6- carbonyls caproic acid (138.2mg, 86%) (petroleum ether:Ethyl acetate=5:1 to 2:1).1H NMR(400MHz,CDCl3)δ9.10(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)δ179.3,173.8,51.6,33.6,24.2,24.0.
Embodiment 25：The synthesis of 8- acetoxyl groups octanoic acid
Other operation reference implementation examples 20, raw materials used is 8- acetoxyl groups octanol (187.7mg, 1.0mmol), during reaction Between be 16 hours, obtain sad (188.9mg, the 93%) (petroleum ether of 8- acetoxyl groups:Ethyl acetate=5:1 to 2:1).1H NMR (400MHz,CDCl3) δ 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)δ180.0,171.4,64.5,33.9,28.82,28.78,28.4,25.6,24.5,20.9.
Embodiment 26：The synthesis of tetrahydrofuran -2- formic acid
Other operation reference implementation examples 20, it is raw materials used for tetrahydrofuran-2-methanol (103.0mg, 99% purity, 1.0mmol), the reaction time is 16 hours, obtains tetrahydrofuran -2- formic acid (85.0mg, 73%) (petroleum ether:Ethyl acetate= 5:1 to 2:1).1HNMR(400MHz,CDCl3)δ9.74(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)δ177.8,76.3,69.6,30.1,25.2.
Embodiment 27：The synthesis of thiophene -2- acetic acid
Other operation reference implementation examples 20, raw materials used is Thiophene-2-Ethanol (130.5mg, 98% purity, 1.0mmol), Reaction time is 16 hours, obtains thiophene -2- acetic acid (114.7mg, 81%) (petroleum ether:Ethyl acetate=5:1 to 2:1) (132.0mg,1.0mmol)。1H NMR(400MHz,CDCl3)δ10.90(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)δ177.0,133.9, 127.2126.9,125.3,35.0.
Embodiment 28：The synthesis of the bromo- 1- n-nonanoic acids of 9-
Other operation reference implementation examples 20, raw materials used is the bromo- 1 nonyl alcohols of 9- (228.0mg, 98% purity, 1.0mmol), Reaction time is 16 hours, obtains the bromo- 1- n-nonanoic acids of 9- (233.5mg, 98%) (petroleum ether:Ethyl acetate=5:1 to 3:1).1H NMR(400MHz,CDCl3) δ 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)δ180.5,34.0,33.9,32.7,29.0,28.9,28.5,28.0, 24.5.
Embodiment 29：The synthesis of 2- hexyloxy acetic acid
Other operation reference implementation examples 20, it is raw materials used for 2- hexyloxyethanols (148.5mg, 98% purity, 1.0mmol), the reaction time is 16 hours, obtains 2- hexyloxies acetic acid (147.7mg, 84%) (petroleum ether:Ethyl acetate=5:1 To 2:1).1H NMR(400MHz,CDCl3)δ8.83(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)；13C NMR(100MHz,CDCl3)δ175.7,72.1,67.6,31.5,29.3,25.5,22.5,13.9.
Embodiment 30：The synthesis of 7- octynic acids
Other operation reference implementation examples 20, raw materials used is 7- alkynes -1- octanols (126.2mg, 1.0mmol), reaction time For 16 hours, 7- octynic acids (112.2mg, 80%) (petroleum ether is obtained:Ethyl acetate=5:1 to 2:1).1H NMR(400MHz, CDCl3) δ 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)δ180.1,84.2,68.4,33.9,28.04,27.99,24.1,18.2.IR(neat) ν(cm-1)3298,2940,2864,2117,1707,1461,1413,1278,1225,1141,1085；MS(ESI,Neg)m/z (%):139(M-1)-.
Embodiment 31：The synthesis of 4- pentinoic acids
Other operation reference implementation examples 20, raw materials used is 4- pentyne-1-alcohols (89.1mg, 95% purity, 1.0mmol), Reaction time is 16 hours, obtains 4- pentinoic acids (67.0mg, 68%) (petroleum ether:Ethyl acetate=5:1 to 2:1).Fusing point： DEG C 55.9-57.0 (petrol ether/ethyl acetate recrystallization)；1H NMR(400MHz,CDCl3)δ11.37(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)δ178.3,82.0,69.2,33.1,14.0.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)
Embodiment 32：The synthesis of 10- undecynes acid
Other operation reference implementation examples 20, raw materials used is 10- undecyne -1- alcohol (182.8mg, 1.0mmol), during reaction Between be 16 hours, obtain sour (176.2mg, the 90%) (petroleum ether of 10- undecynes:Ethyl acetate=5:1 to 2:1).Fusing point： DEG C 51.3-52.2 (petrol ether/ethyl acetate recrystallization)；1H NMR(400MHz,CDCl3)δ9.57(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)δ180.4,79.3,75.3,34.1,29.1,28.98,28.96,28.91,28.8,24.6,18.7, 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).
Embodiment 33：The synthesis of 3- trimethyl silicon substrate propiolic acids
Other operation reference implementation examples 20, raw materials used is 3- trimethyl silicon substrate propilolic alcohols (128.6mg, 1.0mmol), instead It is 48 hours between seasonable, obtains 3- trimethyl silicon substrates propiolic acid (92.9mg, 65%) (petroleum ether:Ethyl acetate=5:1).1H NMR(400MHz,CDCl3)δ6.78(brs,1H,COOH),0.26(s,9H,3×CH3)；13C NMR(100MHz,CDCl3)δ 157.4,97.4,93.7,-1.0.
Embodiment 34：The synthesis of hexamethylene -3- alkene -1- formic acid
Other operation reference implementation examples 20, it is raw materials used for hexamethylene -3- alkene -1- methanol (115.9mg, 98% purity, 1.0mmol), the reaction time is 48 hours, obtains hexamethylene -3- alkene -1- formic acid (89.9mg, 70%) (petroleum ether:Ethyl acetate= 5:1)。1H NMR(400MHz,CDCl3)δ11.63(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)δ182.7, 126.7,124.9,39.1,27.1,24.8,24.3.
Embodiment 35：The synthesis of suberic acid
Other operation reference implementation examples 20, raw materials used is ethohexadiol (148.8mg, 98% purity, 1.0mmol), reaction Time is 48 hours, obtains suberic acid (144.4mg, 83%) (ethyl acetate/n-hexane recrystallization).1H NMR(400MHz, DMSO-d6)δ12.00(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)δ174.5,33.6,28.3,24.4.
Embodiment 35：The synthesis of (+)-Clary sage lactone
Other operation reference implementation examples 20, raw materials used for fragrant purple perilla glycol (254.8mg, 1.0mmol), the reaction time is 16 hours, obtain (+)-Clary sage lactone (233.5mg, 93%) (petroleum ether:Ethyl acetate=20:1 to 5:1).Specific rotation [α]D 28.7=46.9 (c=1.00, CHCl3) (literature value:[α]D 20=47 (c=1.01, CHCl3))；1H NMR(400MHz, CDCl3)δ2.41(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)δ176.7,86.2,59.0,56.5,42.0,39.4,38.6,35.9,33.05,32.99, 28.6,21.5,20.8,20.4,18.0,14.9.
Embodiment 36：The synthesis of phthalide
Other operation reference implementation examples 20, raw materials used is adjacent Benzenediol (141.3mg, 98% purity, 1.0mmol), instead It is 16 hours between seasonable, obtains phthalide (88.3mg, 66%) (petroleum ether:Ethyl acetate=15:1 to 10:1).1H NMR (400MHz,CDCl3) δ 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)δ171.1,146.5,134.0, 129.0,125.62,125.57,122.1,69.6.
Embodiment 37：The synthesis of 7- octynic acids
Under oxygen atmosphere (oxygen ball), Fe (NO are sequentially added into Schlenk pipes3)3·9H2O(202.8mg, 0.5mmol), TEMPO (78.3mg, 4.0mmol), NaCl (29.3mg, 0.5mmol), 7- octyne -1- alcohol (631.4mg, 5.0mmol) with 1,2- dichloroethanes (DCE, 20.0mL).Reaction is stirred at room temperature 20 hours, TLC monitoring (petroleum ethers:Acetic acid Ethyl ester=5:1) until reaction is completed.Reactant mixture is filtered by thick short column of silica gel, ether (3 × 40mL) elution.Vacuum is revolved Dry solvent, silica gel column chromatography (petroleum ether：Ethyl acetate=5:1 to 2:1) product 7- octynic acids (599.1mg, 85%) are obtained.1H NMR(400MHz,CDCl3) δ 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)δ180.3,84.2,68.4,33.9,28.02,27.99, 24.1,18.2.
Embodiment 38：The synthesis (oxygen) of cetyl acid
Under oxygen atmosphere (oxygen ball), Fe (NO are sequentially added into 500mL there-necked flasks3)3·9H2O(1.6164g, 4.0mmol), TEMPO (625.3mg, 4.0mmol), KCl (298.4mg, 4.0mmol) and DCE (4.0mL).Then, ten are added Six alkylols (9.8191g, 98% purity, 40.0mmol).Reaction is stirred at room temperature 16 hours, TLC monitoring (petroleum ethers:Second Acetoacetic ester=5:1) until reaction is completed.Reactant mixture is filtered by thick short column of silica gel, ether (4 × 120mL) elution vacuum It is spin-dried for after solvent, crude product recrystallization purifying (first time petroleum ether：Ethyl acetate=10:1 recrystallizes to obtain 8.5404g products, filter Liquid is spin-dried for rear petroleum ether：Ethyl acetate=18:1 recrystallizes to obtain 1.1413g products) obtain cetyl acid (9.6817g, 94%).1HNMR(400MHz,DMSO-d6) δ 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)δ180.8,34.1,31.9,29.69,29.67,29.66,29.59,29.43,29.37,29.2,29.0,24.6, 22.7,14.1.
Embodiment 39：The synthesis (air+oxygen) of cetyl acid
Fe (NO are sequentially added into a 1L there-necked flasks3)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, 40.0mmol).Then, there-necked flask is connected by extraction valve with a 70L air bags.At room temperature after stirring 1.5h, another mouth passes through Extraction valve is connected as oxygen replenishment with a 2L oxygen balls.Reaction continues to stir at room temperature, TLC monitoring (petroleum ethers:Acetic acid second Ester=5:1) until reaction is completed, altogether by 21.5 hours.Reactant mixture is filtered by thick short column of silica gel, ether (4 × 120mL) elution vacuum is spin-dried for after solvent, crude product recrystallization (petroleum ether:Ethyl acetate=15:1) purifying obtains cetyl Sour (9.0540g, 88%).1H NMR(400MHz,DMSO-d6) δ 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)；13C NMR(100MHz,CDCl3)δ180.6,34.1,31.9,29.70,29.69,29.67,29.66,29.65,29.59,29.44, 29.37,29.24,29.1,24.7,22.7,14.1.
Embodiment 40：The synthesis (slow air stream) of cetyl acid
Fe (NO are sequentially added into a 2L there-necked flasks3)3·9H2O(9.6952g,24.0mmol),TEMPO(3.7514g, 24.0mmol), KCl (1.7885g, 24.0mmol) and 1,2- dichloroethanes (DCE, 400mL).It is stirred at room temperature after 10 minutes, plus Enter cetyl alcohol (59.3883g, 98% purity, 40.0mmol) and DCE (100mL).There-necked flask is passed through slowly by extraction valve Air stream, reaction is stirred at room temperature, TLC monitoring (petroleum ethers:Ethyl acetate=5:1) completed until being reacted after 24 hours.Instead Mixture is answered to be filtered by thick short column of silica gel, ether (3 × 500mL) elution vacuum is spin-dried for after solvent, crude product recrystallization (stone Oily ether:Ethyl acetate=20:1) purifying obtains cetyl acid (55.0232g, 89%).1H NMR(400MHz,DMSO-d6)δ 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)δ180.5,34.1,31.9, 29.67,29.65,29.64,29.62,29.57,29.42,29.35,29.2,29.0,24.7,22.7,14.1.
Embodiment 41：The synthesis of lauric acid/dodecanoic acid
Under oxygen atmosphere (oxygen ball), by Fe (NO3)3·9H2O (40.4mg, 0.10mmol), 2,2,6,6- tetramethyls Piperidines nitrogen oxides (TEMPO, 15.5mg, 0.10mmol), KCl (7.5mg, 0.10mmol), lauric aldehyde (184.3mg, 1.0mmol) it is added to 1,2- dichloroethanes (DCE, 4mL) in Schlenk pipes.12h is stirred at room temperature, TLC monitorings are until reaction Complete.Reactant mixture is filtered through thick short column of silica gel, ether (75mL) elution, is concentrated to give crude product.The crude product passes through silica gel Column chromatography (petroleum ether：Ethyl acetate=5:1) corresponding lauric acid/dodecanoic acid (187.9mg, 94%) is obtained.Fusing point：43-44 DEG C of (oil Ether/re-crystallizing in ethyl acetate) (literature value：43-44℃)；1H NMR(400MHz,CDCl3) δ=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)δ180.6,34.1,31.9,29.6,29.4,29.3, 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.
Embodiment 42：The synthesis of hexahydrobenzoid acid
Other operation reference implementation examples 41, raw materials used is hexamethylene aldehyde, and the reaction time is 12 hours, obtains hexahydrobenzoid acid (115.4mg, 90%) (petroleum ether：Ethyl acetate=5:1).1H NMR(400MHz,CDCl3) δ=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,Hd and Hg)；13C NMR(100MHz, CDCl3) δ=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.
Embodiment 43：The synthesis of octanoic acid
Other operation reference implementation examples 41, raw materials used is octanal (128.1mg), and the reaction time is 12 hours, obtains pungent Sour (138.4mg, 96%) (petroleum ether：Ethyl acetate=5:1).1H NMR(400MHz,CDCl3)δ11.33(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) δ=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.
Embodiment 44：The synthesis of benzenpropanoic acid
Other operation reference implementation examples 41, raw materials used is benzenpropanal (141.3mg, 98% purity, 1.0mmol), reaction Time is 12 hours, obtains benzenpropanoic acid (144.9mg, 96%) (petroleum ether：Ethyl acetate=5:1 to 2:1).1H NMR (400MHz,CDCl3)δ11.56(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)δ179.6, 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.
Embodiment 45：The synthesis of lauric acid/dodecanoic acid
Fe (NO are added in 100mL round-bottomed bottles3)3·9H2O (40.5mg, 0.1mmol) and DCE (4.0mL), is subsequently added into TEMPO (15.6mg, 0.1mmol), KCl (7.5mg, 0.1mmol), lauric aldehyde (183.8mg, 1.0mmol) and DCE (1.0mL). Round-bottomed bottle is connected by extraction valve with air balloon.Reaction is stirred at room temperature 16 hours, until TLC monitoring reactions complete (stone Oily ether:Ethyl acetate=5:1).Reactant mixture is filtered by thick short column of silica gel, and ether (75mL) elution vacuum is spin-dried for solvent Afterwards, silica gel column chromatography (petroleum ether:Ethyl acetate=5:1) purifying obtains lauric acid/dodecanoic acid (176.5mg, 88%).1H NMR (400MHz,CDCl3) δ 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)δ =180.5,34.1,31.9,29.6,29.4,29.3,29.2,29.0,24.6,22.7,14.1.
Embodiment 46：The synthesis of hexahydrobenzoid acid
Other operation reference implementation examples 45, raw materials used is hexahydrobenzaldehyde (112.7mg, 1.0mmol), and the reaction time is 16 hours, obtain hexahydrobenzoid acid (106.4mg, 83%) (petroleum ether：Ethyl acetate=5:1).1H NMR(400MHz,CDCl3) δ=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,Hd and Hg) ；13CNMR(100MHz,CDCl3) δ=182.9,42.9,28.7,25.6,25.3.
Embodiment 47：The synthesis of octanoic acid
Other operation reference implementation examples 45, raw materials used is octanal (128.7mg, 1.0mmol), and the reaction time is 16 small When, obtain sad (139.7mg, 97%) (petroleum ether：Ethyl acetate=5:1).1H NMR(400MHz,CDCl3) δ=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) δ=180.6,34.1,31.6, 29.0,28.9,24.6,22.6,14.0.
Embodiment 48：The synthesis of benzenpropanoic acid
Other operation reference implementation examples 45, raw materials used is benzenpropanal (141.5mg, 98% purity, 1.0mmol), reaction Time is 16 hours, obtains benzenpropanoic acid (147.7mg, 98%) (petroleum ether：Ethyl acetate=5:1 to 2:1).1H NMR (400MHz,CDCl3)δ11.09(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)δ179.5, 140.1,128.5,128.2,126.3,35.6,30.5.
Embodiment 49：(Ra) synthesis of the olefin(e) acids of -7,8- 20 (natural products phlomic acid)
7- octynic acid synthesized references embodiment 30.
The synthesis of 7- methyl 2-octynoates
Substrate 7- octynic acids (981.7mg, 7.0mmol) and Et are added into a round-bottomed bottle2O/MeOH mixed solvents (4/1, 35mL).System is down to 0 DEG C, and TMSCHN is added dropwise2(2.0M, 5.25mL), clear-cutting forestland is to being stirred at room temperature.TLC was shown after 2 hours Reaction is complete.Solvent is removed in rotation.Silica gel column chromatography purifying (petroleum ether/ethyl ether=30/1) obtain 7- methyl 2-octynoates (898.3mg, 83%)：1H NMR(400MHz,CDCl3) δ 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)δ174.0,84.2,68.3,51.4, 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) -7,8- 20 e pioic acid methyl ester synthesis：
Under argon atmospher, CuBr is sequentially added in the tube sealing of drying2(134.1mg, 0.6mmol), (S)-dimethyl dried meat ammonia Alcohol (387.2mg, 3.0mmol), 7- methyl 2-octynoates (694.2mg, 4.5mmol)/dioxane (4.5mL) and lauric aldehyde Tube sealing is tamping by (830.1mg, 4.5mmol)/dioxane (4.5mL) with Teflon stopper, is placed in what is heated in advance Stirred 12 hours in 130 DEG C of oil baths.TLC points plate monitors (petroleum ether/ethyl ether=5/1).The mixture of gained 90mL Et2O is dilute Release, washed with 60mL 3M hydrochloric acid solution.Divide liquid, aqueous phase 30 × 3mL Et2O is extracted.Organic phase merges, and saturation NaCl is molten Liquid is washed, anhydrous Na SO4Dry.Filter, be spin-dried for, silica gel column chromatography (petroleum ether/ethyl ether=100/1) isolated (Ra)-7,8- 20 e pioic acid methyl esters (565.2mg, 58%).95%ee (HPLC conditions:Chiralcel PA-H column, Hexane/i-PrOH=100/0,1.0mL/min, λ=214nm, tR(major)=17.2min, tR(minor)= 22.1min)；[α]D 30.6=-36.8 (c=1.015, CHCl3)；1H NMR(400MHz,CDCl3)δ5.11-5.00(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)；13C NMR(100MHz,CDCl3)δ203.8,174.2,91.1,90.5,51.4,34.0,31.9,29.65,29.63,29.62, 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 (Ra) -7,8- 20 olefin(e) acid (phlomic acid) synthesis：
KOH (141.0mg, 2.5mmol), mixed solvent (5mL, MeOH/H are sequentially added in round-bottomed bottle2O=4/1), and (Ra) 20 e pioic acid methyl esters (322.0mg, 1mmol) of -7,8-/mixed solvent (5mL, MeOH/H2O=4/1).System is at 60 DEG C React complete after lower stirring, TLC monitorings, 2h.System is placed in ice bath, and 3M HCl (ca.1mL) are added dropwise.MeOH is removed in rotation, is added 30mL CH2Cl2With 25mL water.Divide liquid, organic phase separation, aqueous phase CH2Cl2(15mL × 3) are extracted.Merge organic phase, saturation NaCl solution is washed, and anhydrous Na SO4 is dried.Filter, be spin-dried for, silica gel column chromatography (petroleum ether/ethyl ether=10/1 to 2/1) is separated To natural products phlomic acid (283.6mg, 92%).1H NMR(400MHz,CDCl3)δ11.7(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)；13C NMR(100MHz,CDCl3)δ203.8,180.5,91.1,90.5,34.1,31.9,29.67,29.66,29.64,29.5, 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.
Esterification, which derives, determines product (Ra) -7,8- 20 olefin(e) acid (phlomic acid) ee values：
Into a round-bottomed bottle add natural products phlomic acid (55.9mg, 0.2mmol) and mixed solvent (5mL, Et2O/MeOH=4/1).System is cooled to after 0 DEG C, and 0.2mL TMSCHN are added dropwise2(2M in hexane,0.4mmol).Remove ice Bath, reactant mixture clear-cutting forestland room temperature.React complete after TLC monitoring reactions, 2.5h.Solvent, silica gel column chromatography (oil are removed in rotation Isolated liquid (the R of ether/ether=100/1)a) 20 e pioic acid methyl esters (63.1mg, 97%) of -7,8-.96%ee (HPLC conditions:Chiralcel PA-H column, hexane/i-PrOH=100/0,1.0mL/min, λ=214nm, tR (major)=23.7min, tR(minor)=32.3min)；[α]D 30.5=-39.9 (c=0.99, CHCl3)；1H NMR (400MHz,CDCl3) δ 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)δ203.8,174.2,91.1,90.6,51.4, 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.
Embodiment 50:The synthesis of lauric acid/dodecanoic acid (ten diperoxies acid)
Under oxygen atmosphere (oxygen ball), by Fe (NO3)3·9H2O (40.7mg, 0.10mmol), lauric aldehyde (184.2mg, 1.0mmol) it is added to 1,2- dichloroethanes (DCE, 4mL) in Schlenk pipes.12h is stirred at room temperature, TLC monitorings are until reaction Complete.Reactant mixture is filtered through thick short column of silica gel, ether (75mL) elution, is concentrated to give crude product.Add the μ L of methylene bromide 35 Make internal standard, the quantitative hydrogen spectrum of nuclear-magnetism (1H NMR) measure lauric acid/dodecanoic acid yield be 78%, ten diperoxies acid yield be 11%.This is thick Product passes through silica gel column chromatography (petroleum ether:Ethyl acetate=20:1 to 5:1) lauric acid/dodecanoic acid and ten diperoxies acid are obtained.Lauric acid/dodecanoic acid：1H NMR(400MHz,CDCl3) δ 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) δ=180.6,34.1,31.9,29.6,29.4,29.3,29.2,29.0,24.6,22.7,14.1. ten diperoxies acid：1H NMR(400MHz,CDCl3)δ11.38(brs,1H,CO3), H 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) δ=174.7,31.9,30.4,29.54,29.51,29.32,29.29,29.0,28.9,24.6,2 2.7,14.1.

Claims (14)

1. a kind of method of dioxygen oxidation alcohol or aldehyde, it is characterised in that at room temperature, in organic solvent, oxygen is used as using oxygen Agent, using alcohol, glycol or aldehyde as raw material, with ferric nitrate, 2,2,6,6- tetramethyl piperidine nitrogen oxides, inorganic halides are as urging Agent, reacts in neutral conditions, the alcohol or oxidation of aldehydes generation acid, the glycol oxidation generation lactone or diacid；Wherein,
The raw alcohol is R1CH2OH；R1Carbochain including C1-C16, C3-C8 carbocyclic ring or heterocycle, containing fluorine, chlorine, bromine, iodine, Aryl, heterocycle, ester group, ehter bond, alkynyl, the alkyl of double bond functional group, terpene, steroidal structure；
The raw material glycol includes Isosorbide-5-Nitrae-glycol, 1,5- glycol and 1,8- glycol；
The raw material aldehyde is R2CHO；R2Carbochain including C1-C16, C3-C8 carbocyclic ring or heterocycle, contains fluorine, chlorine, bromine, iodine, virtue Base, heterocycle, ester group, ehter bond, alkynyl, the alkyl of double bond functional group, terpene, steroidal structure.
2. a kind of method of dioxygen oxidation alcohol or aldehyde, it is characterised in that at room temperature, in organic solvent, oxygen is used as using oxygen Agent, using aldehyde as raw material, using ferric nitrate as catalyst, reacts in neutral conditions, oxidation of aldehydes the generation acid and peroxy acid；
Wherein, the raw material aldehyde is R2CHO；R2Carbochain including C1-C16, C3-C8 carbocyclic ring or heterocycle, containing fluorine, chlorine, bromine, Iodine, aryl, heterocycle, ester group, ehter bond, alkynyl, the alkyl of double bond functional group, terpene, steroidal structure.
3. the method for dioxygen oxidation alcohol as claimed in claim 1 or 2 or aldehyde, it is characterised in that the aryl is phenyl, alkoxy Phenyl, nitrobenzophenone, halogenophenyl, thienyl, furyl or naphthyl；The alkoxyl phenyl is methoxyphenyl, ethyoxyl Phenyl, the halogenophenyl is difluorophenyl, chlorophenyl, bromo phenyl, iodine substituted phenyl；
The heterocycle is furan nucleus, thiphene ring.
4. the method for dioxygen oxidation alcohol as claimed in claim 2 or aldehyde, it is characterised in that the raw material aldehyde, ferric nitrate mol ratio For 100~10:1.
5. the method for dioxygen oxidation alcohol as claimed in claim 1 or aldehyde, it is characterised in that the raw material, ferric nitrate, 2,2,6,6- Tetramethyl piperidine nitrogen oxides, the mol ratio of inorganic halides are 100:1~10:1~20:1~10.
6. the method for dioxygen oxidation alcohol as claimed in claim 5 or aldehyde, it is characterised in that the raw material, ferric nitrate, 2,2,6,6- Tetramethyl piperidine nitrogen oxides, the mol ratio of inorganic halides are 100:10:20:10.
7. the method for dioxygen oxidation alcohol as claimed in claim 1 or aldehyde, it is characterised in that the inorganic halides be lithium halide, Sodium halide, potassium halide, rubidium halide, caesium halide, halogen atom are fluorine, chlorine, bromine, iodine.
8. the method for dioxygen oxidation alcohol as claimed in claim 7 or aldehyde, it is characterised in that the inorganic halides be potassium chloride, Sodium chloride.
9. the method for dioxygen oxidation alcohol as claimed in claim 1 or aldehyde, it is characterised in that the time of the reaction is that 1-48 is small When.
10. the method for dioxygen oxidation alcohol as claimed in claim 1 or aldehyde, it is characterised in that the oxygen is pure oxygen or sky Oxygen in gas.
11. the method for dioxygen oxidation alcohol as claimed in claim 1 or aldehyde, it is characterised in that the neutrallty condition refer to without Bronsted acid or alkali.
12. the method for dioxygen oxidation alcohol as claimed in claim 1 or aldehyde, it is characterised in that the organic solvent be ethyl acetate, Dichloromethane, 1,2- dichloroethanes, 1,1- dichloroethanes, 1,2- dichloropropanes, 1,3- dichloropropanes, nitromethane, ethylene glycol One or more mixing in dimethyl ether, dioxane, tetrahydrofuran, acetonitrile, benzene or toluene.
13. the method for dioxygen oxidation alcohol as claimed in claim 1 or 2 or aldehyde, it is characterised in that during the oxygen can be air Oxygen；
Wherein, the method used during blowing air is the main source using air bag as oxygen, after reacting 1.5 hours, increases oxygen Balloon is used as supplement；Or by slow air stream method, air is slowly flowed across reaction vessel.
14. one kind synthesis (RaThe method of the olefin(e) acids of) -7,8- 20, it is characterised in that described (Ra) 20 olefin(e) acids of -7,8- Structure such as formula (I) shown in, methods described includes：
(1) using 7- octyne -1- alcohol as raw material, with ferric nitrate, 2,2,6,6- tetramethyl piperidine nitrogen oxides, inorganic halides are to urge Agent, occurs oxidation reaction and obtains 7- octynic acids；
(2) methylation reaction is carried out to 7- octynic acids prepared by step (1), obtains 7- methyl 2-octynoates；
(3) the 7- methyl 2-octynoates prepared by copper bromide, dimethyl dried meat ammonia alcohol catalysis step (2), occur EATA reactions, obtain Join e pioic acid methyl ester；
(4) in the presence of potassium hydroxide, in methanol/water system, connection e pioic acid methyl ester prepared by hydrolysing step (3) obtains axle hand Property connection olefin(e) acid (Ra) 20 olefin(e) acids of -7,8-；
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