CN106588644A - Synthesis method of carboxylic ester compound - Google Patents
Synthesis method of carboxylic ester compound Download PDFInfo
- Publication number
- CN106588644A CN106588644A CN201611006903.6A CN201611006903A CN106588644A CN 106588644 A CN106588644 A CN 106588644A CN 201611006903 A CN201611006903 A CN 201611006903A CN 106588644 A CN106588644 A CN 106588644A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- aldehyde
- nmr
- dichloromethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three 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
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- 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
- C07D333/26—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 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
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthesis method of an ester compound represented by the formula (1), the formula (2) or the formula (3), wherein the method comprises the steps: dissolving an aldehyde compound, sodium azide, tetrabutylammonium iodide and a halogenated compound in a solvent, or directly dissolving an aldehyde compound, sodium azide and tetrabutylammonium iodide in a halogenated compound, carrying out a reaction for 1-12 h at the temperature of 90-100 DEG C, and after the reaction is finished, postprocessing the reaction liquid to obtain the compound represented by the formula (1). The synthesis method has the advantages of mild reaction conditions, no participation of strong acids, strong alkalis or metals, simpliness, high efficiency, high yield, wide application range of substrates, amplified production potential, and relatively large potential economic value.
Description
(1) technical field
The present invention relates to a kind of synthetic method of carboxylic acid ester compound.
(2) background technology
Carboxylate is a kind of important organic chemical industry's intermediate and pharmaceutical intermediate, in research report in recent years, majority
Researcher makees oxidative esterification catalyst using noble metal, expensive.The synthetic method of traditional ester type compound concentrates on carboxylic acid
Prepare under strong acid or basic conditions with alcohol, but the use of strong acid and strong base is unfavorable for environmental conservation and to producing equipment requirements
Height, environmental protection pressure is big.Meanwhile, such synthetic method is not suitable for the system of some special ester type compounds sensitive to acid or alkali
It is standby.Some researcheres employ homogeneous catalyst, have the advantages that high-activity high-selectivity in the reaction, but consumption is big, and
It is difficult to be separated with product and reagent after reaction；The residue problem of poisonous and harmful heavy metallic is also there is simultaneously, constrains it in work
Practical application in industry production.Therefore, in order to promote the development that further oxidative esterification is studied, with aldehyde as Material synthesis ester
Using very extensively in the synthesis of organic chemical industry's intermediate, the route for generating ester by aldehyde has various to method, can be oxidized to carboxylic acid
Afterwards with alcohol direct esterification, or change into after carboxylate with active alkyl halide reaction etc., in recent years, with aldehyde and the step oxide ester of alcohol one
It is combined to the concern that ester causes some scholars.
Carboxylate is a kind of important organic chemical industry's intermediate and pharmaceutical intermediate,
The main component of chocolate
The main component of Mel
The main component of Rhizoma et radix valerianae
The main component of caramel
The main component of plastic plasticizer
Therefore, the present invention adopts oxidant, reacts in the case where relatively mild condition passes through, and explores an easy conjunction
Into the route of carboxylic acid ester compound, reaction equation is as follows：
(3) content of the invention
It is an object of the invention to provide a kind of synthetic method of carboxylic acid ester compound.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of method of asymmetric synthesis of the carboxylic acid ester compound as shown in formula (1), formula (2) or formula (3), described conjunction
Specifically carry out as follows into method：
Aldehyde compound, tetrabutylammonium iodide, Hydrazoic acid,sodium salt, oxidant tert-butyl hydroperoxide and halogenated alkane are dissolved in
In organic solvent, 1～12h is reacted at 90 DEG C, after reaction terminates, reactant liquor is post-treated to obtain formula (1), formula (2) or formula (3)
Shown compound；The amount of the material of the aldehyde, tetrabutylammonium iodide, Hydrazoic acid,sodium salt, tert-butyl hydroperoxide and halogenated alkane
Ratio be 1：0.1～0.2：2-3：1.5～6：2～5；The C atoms number of described halogenated alkane is 1～5；
Wherein：In formula (1), formula (2) or formula (3), the R1For C1～4Alkyl, methoxyl group, nitro, phenyl, naphthyl, halogen
Or trifluoromethyl；The R2For C1～4The phenyl that alkyl, benzyl, phenyl or alkyl, halogen atom replace；The R3For H, methyl, second
Base or chain-like alkyl；The R4For C1～4The phenyl that alkyl, benzyl, phenyl or alkyl, halogen atom replace；Described aldehydes chemical combination
Thing is the aldehyde with aromatics property.
Further, described aldehyde compound is：P-methoxybenzal-dehyde, m-methoxybenzaldehyde, O-methoxy benzene first
Aldehyde, p-tolyl aldehyde, a tolyl aldehyde, o-tolualdehyde, paranitrobenzaldehyde, m-nitrobenzaldehyde, ortho-nitrophenyl
Formaldehyde, 2- naphthaldehydes, furfural, 5- methylfuran aldehyde, 2 thiophene carboxaldehyde or o-phthalaldehyde(OPA).
Further, described halogenated alkane is：Dichloromethane, carbon tetrachloride, benzyl chloride, cylite, iodomethane, dibromo second
Alkane, 1,2- dichloroethanes, n-butyl bromide, allyl chloride, bromopropyl bromine or allyl iodide.
Further, described organic solvent is toluene, tetrahydrofuran, DMF or benzene.
Further, the volumetric usage of the organic solvent is calculated as 0.2～2mL/mmol with the amount of the material of aldehyde.
Further, the method for the reactant liquor post processing is：After reaction terminates, reactant liquor is extracted with dichloromethane, extraction
Take liquid and be dried vacuum removal, after solvent under reduced pressure concentration, gained concentrate carries out column chromatography for separation, eluting with 200～300 mesh silica gel
Agent is ethyl acetate and petroleum ether volume ratio 1:20 mixed liquor, collects the eluent containing target compound, and concentrate drying is obtained
Compound shown in formula (1), formula (2) or formula (3).
More specifically, described ester type compound is one of following：4- methoxybenzoic acid benzyl esters, 4- methoxybenzene first
Sour methyl ester, 4- methoxy ethylbenzoates, 4- methoxybenzoic acid butyl esters, 4- methoxybenzoic acid allyl esters, 4- methoxybenzenes
Formic acid chloroethene ester, 4- ((4- methoxy-benzyls) epoxide) benzyl -4- methoxyl methyl benzoates, 4- methoxybenzoic acid tribromo first
Ester, 2- ar-Toluic acid chloromethyl esters, 3- ar-Toluic acid chloromethyl esters, 4- ar-Toluic acid chloromethyl esters, 2- nitrobenzoic acid chloromethanes
Ester, 3- nitrobenzoic acid chloromethyl esters, 4- nitrobenzoic acid chloromethyl esters, 2-methoxybenzoic acid chloromethyl ester, 3- methoxybenzoic acids
Chloromethyl ester, 4- methoxybenzoic acid chloromethyl esters, 4- ethyl benzoate chloromethyl esters, 2- thiophenic acid chloromethyl esters, di-2-ethylhexylphosphine oxide (thiophene
Fen -2- carboxylates), 2- naphthoic acid chloromethyl esters, 2- furancarboxylic acid chloromethyl esters, 5- methylfuran -2- monochlorome-thylchloroformates or the tert-butyl group
(chloromethyl) phthalic acid.
The carboxylic acid ester compound that the present invention is prepared has antibiotic property, pesticidal, antitumor and arrhythmia etc.
Biological activity, can be used as the important as precursors of medicine.
Compared with prior art, beneficial effect of the present invention is mainly reflected in：
(1) ester type compound of the present invention has chirality, is the critically important medicine intermediate of a class, is widely present
In medicine and natural product skeleton, space is had a wide range of applications.
(2) synthetic method of the invention, simple to operate, and reaction condition is gentle, shows good response characteristic, and reaction is received
Rate is high.
(3) use of traditional esterifications reaction strong acid or basic conditions is avoided in synthetic method of the invention, while also
Environmentally friendly without the need for the participation of poisonous and harmful metal, equipment requirements are lower, and production environmental protection pressure is less.
(4) inventive substrate is applied widely, for aromatic aldehyde, heteroaromatic aldehyde, complicated aromatic aldehyde work well；Together
When various chain halogenated hydrocarbons, cyclic halo hydrocarbon, compound fragrant hydrocarbon can realize outstanding yield, have wide range of applications, have
There is extraordinary economic worth.
(5) synthesis material of the invention is cheap and easily-available, it is adaptable to structure it is complex with special biological activity esters
The efficient preparation of compound, is with a wide range of applications, and is effective supplement of traditional esterifications reaction.
Further, a kind of preparation method of the carboxylic acid ester compound as shown in formula (1), formula (2) or formula (3), the side
Method can also be carried out as follows：
Tetrabutylammonium iodide, Hydrazoic acid,sodium salt and oxidant tert-butyl hydroperoxide are added in aldehyde compound, halogen is dissolved in
In for alkane, 1～12h is reacted at 90～100 DEG C, after reaction terminates, reactant liquor is post-treated to obtain formula (1), formula (2) or formula
(3) compound shown in；The material of the aldehyde compound, tetrabutylammonium iodide, Hydrazoic acid,sodium salt and tert-butyl hydroperoxide
The ratio of amount is 1：0.1～0.2：2～3：1.5～6；The C atoms number of described halogenated alkane is 1～5；
Wherein：In formula (1), formula (2) or formula (3), the R1For C1～4Alkyl, methoxyl group, nitro, phenyl, naphthyl, halogen
Or trifluoromethyl；The R2For C1～4The phenyl that alkyl, benzyl, phenyl or alkyl, halogen atom replace；The R3For H, methyl, second
Base or other chain-like alkyls；The R4For C1～4The phenyl that alkyl, benzyl, phenyl or alkyl, halogen atom replace；Described aldehydes
Compound is the aldehyde with aromatics property.
Further, described aldehyde compound is：P-methoxybenzal-dehyde, m-methoxybenzaldehyde, O-methoxy benzene first
Aldehyde, p-tolyl aldehyde, a tolyl aldehyde, o-tolualdehyde, paranitrobenzaldehyde, m-nitrobenzaldehyde, ortho-nitrophenyl
Formaldehyde, 2- naphthaldehydes, furfural, 5- methylfuran aldehyde, 2 thiophene carboxaldehyde or o-phthalaldehyde(OPA).
Further, described halogenated alkane is：Dichloromethane, chloroform, carbon tetrachloride, benzyl chloride, cylite, iodine first
Alkane, bromoethane, 1,2- dichloroethanes, n-butyl bromide, allyl chloride, bromopropyl bromine or allyl iodide.
Further, the method for the reactant liquor post processing is：After reaction terminates, reactant liquor is extracted with dichloromethane, extraction
Take liquid and be dried vacuum removal, after solvent under reduced pressure concentration, gained concentrate carries out column chromatography for separation, eluting with 200～300 mesh silica gel
Agent is ethyl acetate and petroleum ether volume ratio 1:20 mixed liquor, collects the eluent containing target compound, and concentrate drying is obtained
Compound shown in formula (1), formula (2) or formula (3).
More specifically, described ester type compound is one of following：4- methoxybenzoic acid benzyl esters, 4- methoxybenzene first
Sour methyl ester, 4- methoxy ethylbenzoates, 4- methoxybenzoic acid butyl esters, 4- methoxybenzoic acid allyl esters, 4- methoxybenzenes
Formic acid chloroethene ester, 2- ar-Toluic acid chloromethyl esters, 3- ar-Toluic acid chloromethyl esters, 4- ar-Toluic acid chloromethyl esters, 2- Nitrobenzol
Monochlorome-thylchloroformate, 3- nitrobenzoic acid chloromethyl esters, 4- nitrobenzoic acid chloromethyl esters, 2-methoxybenzoic acid chloromethyl ester, 3- methoxies
Yl benzoic acid chloromethyl ester, 4- methoxybenzoic acid chloromethyl esters, 4- ethyl benzoate chloromethyl esters, 2- thiophenic acid chloromethyl esters, methylene
Base double (thiophene-2-carboxylic acid ester), 2- naphthoic acid chloromethyl esters, 2- furancarboxylic acid chloromethyl esters, 5- methylfuran -2- monochlorome-thylchloroformates or
The tert-butyl group (chloromethyl) phthalic acid.
The carboxylic acid ester compound that the present invention is prepared has antibiotic property, pesticidal, antitumor and arrhythmia etc.
Biological activity, can be used as the important as precursors of medicine.
Compared with prior art, beneficial effect of the present invention is mainly reflected in：
(1) carboxylic acid ester compound of the present invention has chirality, is the critically important medicine intermediate of a class, extensively
In being present in medicine and natural product skeleton, space is had a wide range of applications.
(2) synthetic method of the invention, simple to operate, and reaction condition is gentle, shows good response characteristic, and reaction is received
Rate is high.
(3) use of traditional esterifications reaction strong acid or basic conditions is avoided in synthetic method of the invention, while also
Environmentally friendly without the need for the participation of poisonous and harmful metal, equipment requirements are lower, and production environmental protection pressure is less.
(4) inventive substrate is applied widely, for aromatic aldehyde, heteroaromatic aldehyde, complicated aromatic aldehyde work well；Together
When various chain halogenated hydrocarbons, cyclic halo hydrocarbon, compound fragrant hydrocarbon can realize outstanding yield, have wide range of applications, have
There is extraordinary economic worth.
(5) synthesis material of the invention is cheap and easily-available, it is adaptable to structure it is complex with special biological activity esters
The efficient preparation of compound, is with a wide range of applications, and is effective supplement of traditional esterifications reaction.
(4) specific embodiment
Below by specific embodiment, the invention will be further described, but protection scope of the present invention is not limited in
This.
Embodiment 1：The preparation of 4- methoxybenzoic acid benzyl esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with benzyl chloride (139.24mg, 1.1mmol), solvent toluene (1.0mL) adds little magneton, after 100 DEG C of reaction 2h,
Dichloromethane (3 × 10mL) is extracted, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300
Mesh column chromatography silica gel is filler, and column chromatography for separation purifies the target product (118.50mg, yield 89%) for obtaining.
1HNMR(500MHz,CDCl3):δ=8.04-8.02 (m, 2H), 7.44-7.43 (m, 2H), 7.39-7.36 (m,
2H),7.34-7.31(ddd,1H),5.33(s,2H),3.83(s,3H)；13CNMR(125MHz,CDCl3):δ=166.21,
163.47,136.34,131.77,128.59,128.16,128.12,122.57,113.65,66.41,55.43ppm；
Embodiment 2：The preparation of 4- methoxyl methyl benzoates
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol), and iodomethane (156.15mg, 1.1mmol) solvent toluene (1.0mL), little magneton is added, after 90 DEG C of reaction 2h,
Dichloromethane (3 × 10mL) is extracted, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300
Mesh column chromatography silica gel is filler, and column chromatography for separation purifies the target product (76.71mg, yield 84%) for obtaining.
1H NMR(500MHz,CDCl3):δ=8.00-7.98 (d, 2H), 6.92-6.91 (d, 2H), 3.88 (s, 3H),
3.86(s,3H)；13C NMR(125MHz,CDCl3):δ=166.88,163.33,131.51,122.61,113.60,55.41,
51.86ppm.
Embodiment 3：The preparation of 4- methoxy ethylbenzoates
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) and bromoethane (119.86mg, 1.1mmol), solvent toluene (1.0mL), adds little magneton, 90 DEG C of reaction 2h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (83.19mg, yield 84%) for obtaining.
1H NMR(500MHz,CDCl3):δ=8.01-7.99 (d, 2H), 6.92-6.90 (d, 2H), 4.37-4.32 (q,
2H),3.85(s,3H),1.39-1.36(t,1H)；13C NMR(125MHz,CDCl3):δ=166.41,163.25,131.53,
125.92,122.96,114.01,113.54,60.63,55.40,14.38ppm.
Embodiment 4：The preparation of 4- methoxybenzoic acid butyl esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) and n-butyl bromide (150.72mg, 1.1mmol), solvent toluene (1.0mL), adds little magneton, 90 DEG C of reaction 2h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (97.29mg, yield 85%) for obtaining.
1H NMR(500MHz,CDCl3):δ=8.00-7.99 (d, 2H), 6.92-6.90 (d, 2H), 4.30-4.28 (t,
2H),3.85(s,3H),1.75-1.71(m,2H),1.49-1.45(m,2H),0.99-0.96(t,3H)；13C NMR(125MHz,
CDCl3):δ=166.44,163.25,131.52,125.90,122.98,113.54,77.31,77.06,76 .81,64.52,
55.39,30.84,19.29,13.77ppm.
Embodiment 5：The preparation of 4- methoxybenzoic acid allyl esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) and allyl chloride (84.17mg, 1.1mmol), solvent toluene (1.0mL), adds little magneton, 90 DEG C of reaction 5h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (84.52mg, yield 84%) for obtaining.
1H NMR(500MHz,CDCl3):δ=7.96-7.94 (d, 2H), 6.86-6.84 (d, 2H), 6.00-5.93 (m,
1H),5.35-5.31(ddd,1H),5.22-5.19(dd,1H),4.74-4.72(dt,2H),3.79(s,3H)；13C NMR
(125MHz,CDCl3):δ=165.01,162.38,131.46,130.65,121.56,116.95,112.60,64.25,
54.41ppm；
Embodiment 6：The preparation of 4- methoxybenzoic acid allyl esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with allyl bromide, bromoallylene (116.53mg, 1.1mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 5h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (84.52mg, yield 84%) for obtaining.
1H NMR(500MHz,CDCl3):δ=7.96-7.94 (d, 2H), 6.86-6.84 (d, 2H), 6.00-5.93 (m,
1H),5.35-5.31(ddd,1H),5.22-5.19(dd,1H),4.74-4.72(dt, 2H),3.79(s,3H)；13C NMR
(125MHz,CDCl3):δ=165.01,162.38,131.46,130.65,121.56,116.95,112.60,64.25,
54.41ppm
Embodiment 7：The preparation of 4- methoxybenzoic acid allyl esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with allyl iodide (169.32mg, 1.1mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 5h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (80.49mg, yield 80%) for obtaining.
1H NMR(500MHz,CDCl3):δ=7.96-7.94 (d, 2H), 6.86-6.84 (d, 2H), 6.00-5.93 (m,
1H),5.35-5.31(ddd,1H),5.22-5.19(dd,1H),4.74-4.72(dt,2H),3.79(s,3H)；13C NMR
(125MHz,CDCl3):δ=165.01,162.38,131.46,130.65,121.56,116.95,112.60,64.25,
54.41ppm
Embodiment 8：The preparation of 4- methoxybenzoic acid chloroethene esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) and 1,2- dichloroethanes (108.75mg, 1.1mmol), solvent toluene (1.0mL), adds little magneton, and 90 DEG C anti-
After answering 6h, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation uses ethyl acetate：Petroleum ether=1:30 solvents are eluting
Agent, 300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (100.06mg, yield 85%) for obtaining.
1H NMR(500MHz,CDCl3):δ=8.03-8.01 (d, 2H), 6.94-6.92 (d, 2H), 4.55-4.53 (t,
2H),3.87(s,3H),3.82-3.79(t,3H)；13C NMR(125MHz,CDCl3):δ=165.92,163.63,131.82,
125.93,122.01,113.71,64.19,55.46,41.81ppm.
Embodiment 9：The preparation of 4- ((4- methoxy-benzyls) epoxide) benzyl -4- methoxyl methyl benzoates
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) and to bromobenzyl bromine (136.33mg, 0.55mmol), solvent toluene (1.0mL), little magneton, 90 DEG C of reactions are added
After 6h, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation uses ethyl acetate：Petroleum ether=1:30 solvents are eluting
Agent, 300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (170.38mg, yield 79%) for obtaining.
1H NMR(500MHz,CDCl3):δ=8.21-8.19 (d, 2H), 8.02-8.00 (d, 2H), 7.51-7.49 (d,
2H),7.32-7.30(d,2H),6.96-6.91(m,4H),5.28(s,2H),3.90(s,3H),3.86(s,3H)；13C NMR
(125MHz,CDCl3):δ=166.06,164.60,163.56,135.35,132.00,131.75,131.72,129.80,
125.93,122.28,114.02,113.69,65.60,55.97,55.46ppm；
Embodiment 10：The preparation of 4- methoxybenzoic acid tribromo methyl ester
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with carbon tetrabromide (356.04mg, 1.10mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 3h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (173.71mg, yield 75%) for obtaining.
1H NMR(500MHz,CDCl3):δ=7.94-7.92 (d, 2H), 6.90-6.88 (d, 2H), 7.51-7.49 (d,
2H),3.77(s,3H)；13C NMR(125MHz,CDCl3):δ=164.61,161.93,130.35,112.36,79.51,
54.38,27.24ppm.
Embodiment 11：The preparation of 2- ar-Toluic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 2- tolyl aldehydes (66.0mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) and dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL), adds little magneton, 90 DEG C of reaction 2h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column layer chromatography silicone rubbers are filler, and column chromatography for separation purifies the target product (78.95mg, yield 78%) for obtaining,1H NMR
(500MHz,CDCl3):δ=8.00-7.98 (d, 1H), 7.47-7.44 (td, 1H), 7.29-7.28 (d, 2H), 5.38 (s,
2H),2.64(s,3H)；13C NMR(125MHz,CDCl3):δ=165.63,140.09,131.81,130.91,129.95,
124.86,73.79,28.68,20.84ppm；
Embodiment 12：The preparation of 3- ar-Toluic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 3- tolyl aldehydes (66.0mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 12h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (71.86mg, yield 71%) for obtaining.
1H NMR(500MHz,CDCl3):δ=7.83-7.80 (m, 2H), 7.35-7.34 (d, 1H), 7.30-7.27 (t,
1H),5.31(s,2H),2.34(s,3H)；13C NMR(125MHz,CDCl3):δ=165.24,137.41,133.50,
129.46,127.81,127.44,126.08,74.06,20.23ppm.
Embodiment 13：The preparation of 4- ar-Toluic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 4- tolyl aldehydes (66.0mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 12h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (79.96mg, yield 79%) for obtaining.
1H NMR(500MHz,CDCl3):δ=7.83-7.80 (m, 2H), 7.35-7.34 (d, 1H), 7.30-7.27 (t,
1H),5.31(s,2H),2.34(s,3H)；13C NMR(125MHz,CDCl3):δ=165.24,137.41,133.50,
129.46,127.81,127.44,126.08,74.06,20.23ppm.
Embodiment 14：The preparation of 2- nitrobenzoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 2- nitrobenzaldehydes (83.1mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 12h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column layer chromatography silicone rubbers are filler, and column chromatography for separation purifies the target product (80.41mg, yield 68%) for obtaining.
1H NMR (500MHz, CDCl3) δ 7.94 (dd, J=7.9,1.5Hz, 1H), 7.58 (dd, J=11.1,4.4Hz,
1H), 7.28 (d, J=8.1Hz, 1H), 7.22 (t, J=7.6Hz, 1H), 5.38 (s, 2H).13C NMR(125MHz,CDCl3)δ
164.5,140.8,134.0,132.2,124.5,119.9,75.2.
Embodiment 15：The preparation of 3- nitrobenzoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 3- nitrobenzaldehydes (83.1mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 12h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (82.78mg, yield 70%) for obtaining.
1H NMR (500MHz, CDCl3) δ 8.92 (d, J=1.6Hz, 1H), 8.51-8.45 (m, 1H), 8.42 (d, J=
7.8Hz, 1H), 7.71 (t, J=8.0Hz, 1H), 5.46 (s, 2H).13C NMR(125MHz,CDCl3)δ163.14,147.36,
134.52,129.72,128.91,127.13,123.93,74.89.
Embodiment 16：The preparation of 4- nitrobenzoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 4- nitrobenzaldehydes (83.1mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) and dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL), adds little magneton, 90 DEG C of reactions
After 12h, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation uses ethyl acetate：Petroleum ether=1:30 solvents are eluting
Agent, 300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (78.05mg, yield 66%) for obtaining.
1H NMR(500MHz,CDCl3)δ8.35–8.30(m,2H),8.29-8.24(m,2H),5.44(s,2H).13C
NMR(125MHz,CDCl3)δ163.33,133.26,130.09,122.72,74.92.
Embodiment 17：The preparation of 2-methoxybenzoic acid chloromethyl ester
Clean 15mL reaction under high pressures bottle is taken, Benzaldehyde,2-methoxy (74.83mg, 0.55mmol), tetrabutyl iodate is added
Ammonium (20.3mg, 0.055mmol), Hydrazoic acid,sodium salt (71.50mg, 1.1mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (93.42mg, 1.10mmol), solvents tetrahydrofurane (1.0mL) adds little magneton, and 90 DEG C anti-
After answering 12h, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation uses ethyl acetate：Petroleum ether=1:30 solvents are to wash
De- agent, 300 mesh column layer chromatography silicone rubbers are filler, and column chromatography for separation purifies the target product (89.11mg, yield 81%) for obtaining.1H NMR (500MHz, CDCl3) δ 7.88 (dd, J=7.9,1.8Hz, 1H), 7.56-7.50 (m, 1H), 7.03-6.97 (m,
2H),5.93(s,2H),3.92(s,3H).13C NMR(125MHz,CDCl3)δ163.4,160.1,134.8,132.2,120.1,
117.8,112.1,69.0,56.0
Embodiment 18：The preparation of 3- methoxybenzoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, m-methoxybenzaldehyde (74.83mg, 0.55mmol), tetrabutyl iodate is added
Ammonium (40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (93.42mg, 1.10mmol), solvent benzol (1.0mL) adds little magneton, 90 DEG C of reaction 12h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column layer chromatography silicone rubbers are filler, and column chromatography for separation purifies the target product (88.00mg, yield 80%) for obtaining.
1H NMR(500MHz,CDCl3) δ 7.68 (dd, J=7.7,1.0Hz, 1H), 7.59 (dd, J=2.5,1.5Hz,
1H), 7.38 (t, J=8.0Hz, 1H), 7.15 (ddd, J=8.3,2.6,0.8Hz, 1H), 5.39 (s, 2H), 3.86 (s, 3H).
13C NMR(125MHz,CDCl3)δ164.98,158.65,129.15,128.59,121.35,119.37,
113.21,74.20,54.47
Embodiment 19：The preparation of 4- methoxybenzoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 4-methoxybenzaldehyde (74.83mg, 0.55mmol), tetrabutyl iodate is added
Ammonium (40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.40mL,
3.3mmol) with dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 10h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column layer chromatography silicone rubbers are filler, and column chromatography for separation purifies the target product (96.80mg, yield 88%) for obtaining.
1H NMR(500MHz,CDCl3) δ 8.04 (d, J=8.9Hz, 2H), 6.95 (d, J=8.9Hz, 2H), 5.37 (s,
2H),3.88(s,3H).13C NMR(125MHz,CDCl3)δ164.73,162.99,131.08,120.20,112.83,73.87,
54.48.
Embodiment 20：The preparation of 4- ethyl benzoate chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 4- ethylo benzene formaldehyde (73.74mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 10h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column layer chromatography silicone rubbers are filler, and column chromatography for separation purifies the target product (87.14mg, yield 80%) for obtaining,
1H NMR(500MHz,CDCl3) δ 8.00 (d, J=8.3Hz, 2H), 7.30 (d, J=8.3Hz, 2H), 5.38 (s,
2H), 2.76-2.68 (q, 2H), 1.25 (d, J=2.5Hz, 3H).13C NMR(125MHz,CDCl3)δ165.10,149.78,
129.10,127.09,125.34,73.96,28.01,14.15.
Embodiment 21：The preparation of 2- thiophenic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 2 thiophene carboxaldehyde (61.60mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 6h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column layer chromatography silicone rubbers are filler, and column chromatography for separation purifies the target product (48.39mg, yield 50%) for obtaining.
1H NMR(500MHz,CDCl3) δ 7.89 (dd, J=3.8,1.2Hz, 1H), 7.64 (dd, J=5.0,1.2Hz,
1H), 7.14 (dd, J=4.9,3.8Hz, 1H), 5.36 (s, 2H).13C NMR(125MHz,CDCl3)δ160.58,133.67,
132.69,127.03,74.16.
Embodiment 22：The preparation of di-2-ethylhexylphosphine oxide (thiophene-2-carboxylic acid ester)
Clean 15mL reaction under high pressures bottle is taken, 2 thiophene carboxaldehyde (61.60mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol), dichloromethane (93.43mg, 1.1mmol) and toluene (1.0mL), add little magneton, after 90 DEG C of reaction 6h, two
Chloromethanes (3 × 10mL) are extracted, organic faciess decompression precipitation, use ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh
Column chromatography silica gel is filler, and column chromatography for separation purifies the target product (76.64mg, yield 50%) for obtaining,
1H NMR(500MHz,CDCl3) δ 7.89 (dd, J=3.8,1.2Hz, 1H), 7.62 (dd, J=5.0,1.2Hz,
1H), 7.12 (dd, J=4.9,3.8Hz, 1H), 6.16 (s, 1H).13C NMR(125MHz,CDCl3)δ159.70,133.77,
132.74,131.23,126.97,78.73.
Embodiment 23：The preparation of 2- naphthoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 2- naphthaldehydes (90.78mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 6h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column layer chromatography silicone rubbers are filler, and column chromatography for separation purifies the target product (95.60mg, yield 79%) for obtaining.
1H NMR(500MHz,CDCl3) δ 8.67 (s, 1H), 8.09 (dd, J=8.6,1.7Hz, 1H), 7.98 (d, J=
8.0Hz, 1H), 7.91 (t, J=8.1Hz, 2H), 7.65-7.60 (m, 1H), 7.58 (dd, J=8.1,1.1Hz, 1H), 5.46
(s,2H).13C NMR(125MHz,CDCl3)δ165.24,134.84,131.39,130.80,128.46,127.70,127.40,
126.80,125.86,125.08,124.11,74.25.
Embodiment 24：The preparation of 2- furancarboxylic acid chloromethyl esters
Take clean 15mL reaction under high pressures bottle, add furfural (52.81mg, 0.55mmol), tetrabutylammonium iodide (40.6mg,
0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL, 0.825mmol)
With dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL), little magneton is added, after 90 DEG C of reaction 3h, dichloromethane
(3 × 10mL) is extracted, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column chromatographies
Silica gel is filler, and column chromatography for separation purifies the target product (71.27mg, yield 81%) for obtaining,
1H NMR(500MHz,CDCl3) δ 7.66-7.63 (m, 1H), 7.30 (d, J=3.5Hz, 1H), 6.56 (dd, J=
3.5,1.7Hz,1H),5.37(s,2H).13C NMR(125MHz,CDCl3)δ156.88,146.25,142.46,118.58,
111.17,73.99.
Embodiment 25：The preparation of 5- methylfuran -2- monochlorome-thylchloroformates
Clean 15mL reaction under high pressures bottle is taken, 5- methylfurans -2- formaldehyde (60.52mg, 0.55mmol), tetrabutyl iodine is added
Change ammonium (40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide
(0.10mL, 0.825mmol) and dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL), the little magneton of addition, 90
DEG C reaction 3h after, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, use ethyl acetate：Petroleum ether=1:30 solvents are
Eluant, 300 mesh column layer chromatography silicone rubbers are filler, and column chromatography for separation purifies target product (74.65mg, the yield for obtaining
78%).
1H NMR(500MHz,CDCl3) δ 7.21 (d, J=3.4Hz, 1H), 6.17 (dd, J=3.4,0.8Hz, 1H), 5.35
(s,2H),2.41(s,3H).13C NMR(125MHz,CDCl3)δ157.45,156.91,140.79,120.20,107.85,
73.77,59.39.
Embodiment 26：The preparation of the tert-butyl group (chloromethyl) phthalic acid
Clean 15mL reaction under high pressures bottle is taken, o-phthalaldehyde(OPA) (73.2mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (93.42mg, 1.10mmol), solvent toluene (1.0mL) adds little magneton, 90 DEG C of reaction 12h
Afterwards, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents are eluant,
300 mesh column chromatography silica gels are filler, and column chromatography for separation purifies the target product (90.82mg, yield 61%) for obtaining.
1H NMR(500MHz,CDCl3) δ 7.72 (dd, J=7.3,1.7Hz, 2H), 7.55 (td, J=6.6,1.6Hz,
2H),5.36(s,2H),1.59(s,9H).13C NMR(125MHz,CDCl3)δ166.30,165.24,132.82,130.50,
129.66,127.99,81.46,74.54,26.94.
Embodiment 27：The preparation of 4- methoxybenzoic acid benzyl esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with benzyl chloride (1.0mL), little magneton is added, after 100 DEG C of reaction 2h, dichloromethane (3 × 10mL) extraction, organic faciess
Decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column chromatography silica gels be filler, column chromatography for separation
The target product (118.50mg, yield 89%) that purification is obtained.
1HNMR(500MHz,CDCl3):δ=8.04-8.02 (m, 2H), 7.44-7.43 (m, 2H), 7.39-7.36 (m,
2H),7.34-7.31(ddd,1H),5.33(s,2H),3.83(s,3H)；13CNMR(125MHz,CDCl3):δ=166.21,
163.47,136.34,131.77,128.59,128.16,128.12,122.57,113.65,66.41,55.43ppm；
Embodiment 28：The preparation of 4- methoxyl methyl benzoates
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol), and iodomethane (1.0mL), little magneton is added, after 90 DEG C of reaction 2h, dichloromethane (3 × 10mL) extraction is organic
Subtract each other pressure-off molten, use ethyl acetate：Petroleum ether=1:30 solvents are eluant, and 300 mesh column chromatography silica gels are filler, and column chromatography divides
From the target product (76.71mg, yield 84%) that purification is obtained.
1H NMR(500MHz,CDCl3):δ=8.00-7.98 (d, 2H), 6.92-6.91 (d, 2H), 3.88 (s, 3H),
3.86(s,3H)；13C NMR(125MHz,CDCl3):δ=166.88,163.33,131.51,122.61,113.60,55.41,
51.86ppm.
Embodiment 29：The preparation of 4- methoxy ethylbenzoates
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) and bromoethane (1.0mL), little magneton is added, after 90 DEG C of reaction 2h, dichloromethane (3 × 10mL) extraction is organic
Subtract each other pressure-off molten, use ethyl acetate：Petroleum ether=1:30 solvents are eluant, and 300 mesh column chromatography silica gels are filler, and column chromatography divides
From the target product (83.19mg, yield 84%) that purification is obtained.
1H NMR(500MHz,CDCl3):δ=8.01-7.99 (d, 2H), 6.92-6.90 (d, 2H), 4.37-4.32 (q,
2H),3.85(s,3H),1.39-1.36(t,1H)；13C NMR(125MHz,CDCl3):δ=166.41,163.25,131.53,
125.92,122.96,114.01,113.54,60.63,55.40,14.38ppm.
Embodiment 30：The preparation of 4- methoxybenzoic acid butyl esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) and n-butyl bromide (1.0mL), little magneton is added, after 90 DEG C of reaction 2h, dichloromethane (3 × 10mL) extraction is organic
Subtract each other pressure-off molten, use ethyl acetate：Petroleum ether=1:30 solvents are eluant, and 300 mesh column chromatography silica gels are filler, and column chromatography divides
From the target product (97.29mg, yield 85%) that purification is obtained.
1H NMR(500MHz,CDCl3):δ=8.00-7.99 (d, 2H), 6.92-6.90 (d, 2H), 4.30-4.28 (t,
2H),3.85(s,3H),1.75-1.71(m,2H),1.49-1.45(m,2H),0.99-0.96 (t,3H)；13C NMR
(125MHz,CDCl3):δ=166.44,163.25,131.52,125.90,122.98,113.54,77.31,77.06,
76.81,64.52,55.39,30.84,19.29,13.77ppm.
Embodiment 31：The preparation of 4- methoxybenzoic acid allyl esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with allyl chloride (1.0mL), little magneton is added, after 90 DEG C of reaction 5h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column chromatography silica gels be filler, column chromatography
The target product (84.52mg, yield 84%) that separating-purifying is obtained.
1H NMR(500MHz,CDCl3):δ=7.96-7.94 (d, 2H), 6.86-6.84 (d, 2H), 6.00-5.93 (m,
1H),5.35-5.31(ddd,1H),5.22-5.19(dd,1H),4.74-4.72(dt,2H),3.79(s,3H)；13C NMR
(125MHz,CDCl3):δ=165.01,162.38,131.46,130.65,121.56,116.95,112.60,64.25,
54.41ppm；
Embodiment 32：The preparation of 4- methoxybenzoic acid allyl esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with allyl bromide, bromoallylene (1.0mL), little magneton is added, after 90 DEG C of reaction 5h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column chromatography silica gels be filler, column chromatography
The target product (84.52mg, yield 84%) that separating-purifying is obtained.
1H NMR(500MHz,CDCl3):δ=7.96-7.94 (d, 2H), 6.86-6.84 (d, 2H), 6.00-5.93 (m,
1H),5.35-5.31(ddd,1H),5.22-5.19(dd,1H),4.74-4.72(dt,2H),3.79(s,3H)；13C NMR
(125MHz,CDCl3):δ=165.01,162.38,131.46,130.65,121.56,116.95,112.60,64.25,
54.41ppm
Embodiment 33：The preparation of 4- methoxybenzoic acid allyl esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with allyl iodide (1.0mL), little magneton is added, after 90 DEG C of reaction 5h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column chromatography silica gels be filler, column chromatography
The target product (80.49mg, yield 80%) that separating-purifying is obtained.
1H NMR(500MHz,CDCl3):δ=7.96-7.94 (d, 2H), 6.86-6.84 (d, 2H), 6.00-5.93 (m,
1H),5.35-5.31(ddd,1H),5.22-5.19(dd,1H),4.74-4.72(dt,2H),3.79(s,3H)；13C NMR
(125MHz,CDCl3):δ=165.01,162.38,131.46,130.65,121.56,116.95,112.60,64.25,
54.41ppm
Embodiment 34：The preparation of 4- methoxybenzoic acid chloroethene esters
Clean 15mL reaction under high pressures bottle is taken, P-methoxybenzal-dehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with 1,2- dichloroethanes (1.0mL), little magneton is added, after 90 DEG C of reaction 6h, dichloromethane (3 × 10mL) extraction
Take, organic faciess decompression precipitation uses ethyl acetate：Petroleum ether=1:30 solvents are eluant, and 300 mesh column chromatography silica gels are filler,
The target product (100.06mg, yield 85%) that column chromatography for separation purification is obtained.
1H NMR(500MHz,CDCl3):δ=8.03-8.01 (d, 2H), 6.94-6.92 (d, 2H), 4.55-4.53 (t,
2H),3.87(s,3H),3.82-3.79(t,3H)；13C NMR(125MHz,CDCl3):δ=165.92,163.63,131.82,
125.93,122.01,113.71,64.19,55.46,41.81ppm.
Embodiment 35：The preparation of 2- ar-Toluic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 2- tolyl aldehydes (66.0mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (1.0mL), little magneton is added, after 90 DEG C of reaction 2h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column layer chromatography silicone rubbers be filler, post layer
The target product (78.95mg, yield 78%) that analysis separating-purifying is obtained,
1H NMR(500MHz,CDCl3):δ=8.00-7.98 (d, 1H), 7.47-7.44 (td, 1H), 7.29-7.28 (d,
2H),5.38(s,2H),2.64(s,3H)；13C NMR(125MHz,CDCl3):δ=165.63,140.09,131.81,
130.91,129.95,124.86,73.79,28.68,20.84ppm；
Embodiment 36：The preparation of 3- ar-Toluic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 3- tolyl aldehydes (66.0mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (1.0mL), little magneton is added, after 90 DEG C of reaction 12h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column chromatography silica gels be filler, column chromatography
The target product (71.86mg, yield 71%) that separating-purifying is obtained.
1H NMR(500MHz,CDCl3):δ=7.83-7.80 (m, 2H), 7.35-7.34 (d, 1H), 7.30-7.27 (t,
1H),5.31(s,2H),2.34(s,3H)；13C NMR(125MHz,CDCl3):δ=165.24,137.41,133.50,
129.46,127.81,127.44,126.08,74.06,20.23ppm.
Embodiment 37：The preparation of 4- ar-Toluic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 4- tolyl aldehydes (66.0mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (1.0mL), little magneton is added, after 90 DEG C of reaction 12h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column chromatography silica gels be filler, column chromatography
The target product (79.96mg, yield 79%) that separating-purifying is obtained.
1H NMR(500MHz,CDCl3):δ=7.83-7.80 (m, 2H), 7.35-7.34 (d, 1H), 7.30-7.27 (t,
1H),5.31(s,2H),2.34(s,3H)；13C NMR(125MHz,CDCl3):δ=165.24,137.41,133.50,
129.46,127.81,127.44,126.08,74.06,20.23ppm；
Embodiment 38：The preparation of 2- nitrobenzoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 2- nitrobenzaldehydes (83.1mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (1.0mL), little magneton is added, after 90 DEG C of reaction 12h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column layer chromatography silicone rubbers be filler, post layer
The target product (80.41mg, yield 68%) that analysis separating-purifying is obtained.
1H NMR (500MHz, CDCl3) δ 7.94 (dd, J=7.9,1.5Hz, 1H), 7.58 (dd, J=11.1,4.4Hz,
1H), 7.28 (d, J=8.1Hz, 1H), 7.22 (t, J=7.6Hz, 1H), 5.38 (s, 2H).13C NMR(125MHz,CDCl3)δ
164.5,140.8,134.0,132.2,124.5,119.9,75.2.
Embodiment 39：The preparation of 3- nitrobenzoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 3- nitrobenzaldehydes (83.1mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (1.0mL), little magneton is added, after 90 DEG C of reaction 12h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column chromatography silica gels be filler, column chromatography
The target product (82.78mg, yield 70%) that separating-purifying is obtained.
1H NMR (500MHz, CDCl3) δ 8.92 (d, J=1.6Hz, 1H), 8.51-8.45 (m, 1H), 8.42 (d, J=
7.8Hz, 1H), 7.71 (t, J=8.0Hz, 1H), 5.46 (s, 2H).13C NMR(125MHz,CDCl3)δ163.14,147.36,
134.52,129.72,128.91,127.13,123.93,74.89.
Embodiment 40：The preparation of 4- nitrobenzoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 4- nitrobenzaldehydes (83.1mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) and dichloromethane (1.0mL), little magneton is added, after 90 DEG C of reaction 12h, dichloromethane (3 × 10mL) extraction,
Organic faciess decompression precipitation, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column chromatography silica gels be filler, post layer
The target product (78.05mg, yield 66%) that analysis separating-purifying is obtained.
1H NMR(500MHz,CDCl3)δ8.35–8.30(m,2H),8.29-8.24(m,2H),5.44(s,2H).13C
NMR(125MHz,CDCl3)δ163.33,133.26,130.09,122.72,74.92.
Embodiment 41：The preparation of 2-methoxybenzoic acid chloromethyl ester
Clean 15mL reaction under high pressures bottle is taken, Benzaldehyde,2-methoxy (74.83mg, 0.55mmol), tetrabutyl iodate is added
Ammonium (20.3mg, 0.055mmol), Hydrazoic acid,sodium salt (71.50mg, 1.1mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (1.0mL), little magneton is added, after 90 DEG C of reaction 12h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column layer chromatography silicone rubbers be filler, post layer
The target product (89.11mg, yield 81%) that analysis separating-purifying is obtained.
1H NMR (500MHz, CDCl3) δ 7.88 (dd, J=7.9,1.8Hz, 1H), 7.56-7.50 (m, 1H), 7.03-
6.97(m,2H),5.93(s,2H),3.92(s,3H).13C NMR(125MHz,CDCl3)δ163.4,160.1,134.8,
132.2,120.1,117.8,112.1,69.0,56.0
Embodiment 42：The preparation of 3- methoxybenzoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, m-methoxybenzaldehyde (74.83mg, 0.55mmol), tetrabutyl iodate is added
Ammonium (40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (1.0mL), little magneton is added, after 90 DEG C of reaction 12h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column layer chromatography silicone rubbers be filler, post layer
The target product (88.00mg, yield 80%) that analysis separating-purifying is obtained.
1H NMR(500MHz,CDCl3) δ 7.68 (dd, J=7.7,1.0Hz, 1H), 7.59 (dd, J=2.5,1.5Hz,
1H), 7.38 (t, J=8.0Hz, 1H), 7.15 (ddd, J=8.3,2.6,0.8Hz, 1H), 5.39 (s, 2H), 3.86 (s, 3H).
13C NMR(125MHz,CDCl3)δ164.98,158.65,129.15,128.59,121.35,119.37,
113.21,74.20,54.47
Embodiment 43：The preparation of 4- methoxybenzoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 4-methoxybenzaldehyde (74.83mg, 0.55mmol), tetrabutyl iodate is added
Ammonium (40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.40mL,
3.3mmol) with dichloromethane (1.0mL), little magneton is added, after 90 DEG C of reaction 10h, dichloromethane (3 × 10mL) extraction is organic
Subtract each other pressure-off molten, use ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column layer chromatography silicone rubbers be filler, column chromatography
The target product (96.80mg, yield 88%) that separating-purifying is obtained.
1H NMR(500MHz,CDCl3) δ 8.04 (d, J=8.9Hz, 2H), 6.95 (d, J=8.9Hz, 2H), 5.37 (s,
2H),3.88(s,3H).13C NMR(125MHz,CDCl3)δ164.73,162.99,131.08,120.20,112.83,73.87,
54.48.
Embodiment 44：The preparation of 4- ethyl benzoate chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 4- ethylo benzene formaldehyde (73.74mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (1.0mL), little magneton is added, after 90 DEG C of reaction 10h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column layer chromatography silicone rubbers be filler, post layer
The target product (87.14mg, yield 80%) that analysis separating-purifying is obtained,
1H NMR(500MHz,CDCl3) δ 8.00 (d, J=8.3Hz, 2H), 7.30 (d, J=8.3Hz, 2H), 5.38 (s,
2H), 2.76-2.68 (q, 2H), 1.25 (d, J=2.5Hz, 3H).13C NMR(125MHz,CDCl3)δ165.10,149.78,
129.10,127.09,125.34,73.96,28.01,14.15.
Embodiment 45：The preparation of 2- thiophenic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 2 thiophene carboxaldehyde (61.60mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (1.0mL), little magneton is added, after 90 DEG C of reaction 6h, dichloromethane (3 × 10mL) extraction has
It is molten that machine subtracts each other pressure-off, uses ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column layer chromatography silicone rubbers be filler, post layer
The target product (48.39mg, yield 50%) that analysis separating-purifying is obtained.
1H NMR(500MHz,CDCl3) δ 7.89 (dd, J=3.8,1.2Hz, 1H), 7.64 (dd, J=5.0,1.2Hz,
1H), 7.14 (dd, J=4.9,3.8Hz, 1H), 5.36 (s, 2H).13C NMR(125MHz,CDCl3)δ160.58,133.67,
132.69,127.03,74.16.
Embodiment 46：The preparation of di-2-ethylhexylphosphine oxide (thiophene-2-carboxylic acid ester)
Clean 15mL reaction under high pressures bottle is taken, 2 thiophene carboxaldehyde (61.60mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol), dichloromethane (1.0mL), adds little magneton, and after 90 DEG C of reaction 6h, dichloromethane (3 × 10mL) extraction is organic
Subtract each other pressure-off molten, use ethyl acetate：Petroleum ether=1:30 solvents are eluant, and 300 mesh column chromatography silica gels are filler, and column chromatography divides
From the target product (76.64mg, yield 50%) that purification is obtained,
1H NMR(500MHz,CDCl3) δ 7.89 (dd, J=3.8,1.2Hz, 1H), 7.62 (dd, J=5.0,1.2Hz,
1H), 7.12 (dd, J=4.9,3.8Hz, 1H), 6.16 (s, 1H).13C NMR(125MHz,CDCl3)δ159.70,133.77,
132.74,131.23,126.97,78.73.
Embodiment 47：The preparation of 2- naphthoic acid chloromethyl esters
Clean 15mL reaction under high pressures bottle is taken, 2- naphthaldehydes (90.78mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (1mL), little magneton is added, after 90 DEG C of reaction 6h, dichloromethane (3 × 10mL) extraction is organic
Subtract each other pressure-off molten, use ethyl acetate：Petroleum ether=1:30 solvents be eluant, 300 mesh column layer chromatography silicone rubbers be filler, column chromatography
The target product (95.60mg, yield 79%) that separating-purifying is obtained.
1H NMR(500MHz,CDCl3) δ 8.67 (s, 1H), 8.09 (dd, J=8.6,1.7Hz, 1H), 7.98 (d, J=
8.0Hz, 1H), 7.91 (t, J=8.1Hz, 2H), 7.65-7.60 (m, 1H), 7.58 (dd, J=8.1,1.1Hz, 1H), 5.46
(s,2H).13C NMR(125MHz,CDCl3)δ165.24,134.84,131.39,130.80,128.46,127.70,127.40,
126.80,125.86,125.08,124.11,74.25.
Embodiment 48：The preparation of 2- furancarboxylic acid chloromethyl esters
Take clean 15mL reaction under high pressures bottle, add furfural (52.81mg, 0.55mmol), tetrabutylammonium iodide (40.6mg,
0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL, 0.825mmol)
With dichloromethane (1mL), little magneton is added, after 90 DEG C of reaction 3h, dichloromethane (3 × 10mL) extraction, organic faciess decompression precipitation,
Use ethyl acetate：Petroleum ether=1:30 solvents are eluant, and 300 mesh column chromatography silica gels are filler, and column chromatography for separation purification is obtained
Target product (71.27mg, yield 81%),
1H NMR(500MHz,CDCl3) δ 7.66-7.63 (m, 1H), 7.30 (d, J=3.5Hz, 1H), 6.56 (dd, J=
3.5,1.7Hz,1H),5.37(s,2H).13C NMR(125MHz,CDCl3)δ156.88,146.25,142.46,118.58,
111.17,73.99.
Embodiment 49：The preparation of 5- methylfuran -2- monochlorome-thylchloroformates
Clean 15mL reaction under high pressures bottle is taken, 5- methylfurans -2- formaldehyde (60.52mg, 0.55mmol), tetrabutyl iodine is added
Change ammonium (40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide
(0.10mL, 0.825mmol) and dichloromethane (1mL), adds little magneton, after 90 DEG C of reaction 3h, dichloromethane (3 × 10mL) extraction
Take, organic faciess decompression precipitation uses ethyl acetate：Petroleum ether=1:30 solvents are eluant, and 300 mesh column layer chromatography silicone rubbers are to fill out
Material, the target product (74.65mg, yield 78%) that column chromatography for separation purification is obtained.
1H NMR(500MHz,CDCl3) δ 7.21 (d, J=3.4Hz, 1H), 6.17 (dd, J=3.4,0.8Hz, 1H), 5.35
(s,2H),2.41(s,3H).13C NMR(125MHz,CDCl3)δ157.45,156.91,140.79,120.20,107.85,
73.77,59.39.
Embodiment 50：The preparation of the tert-butyl group (chloromethyl) phthalic acid
Clean 15mL reaction under high pressures bottle is taken, o-phthalaldehyde(OPA) (73.2mg, 0.55mmol), tetrabutylammonium iodide is added
(40.6mg, 0.11mmol), Hydrazoic acid,sodium salt (107.25mg, 1.65mmol), oxidant tert-butyl hydroperoxide (0.10mL,
0.825mmol) with dichloromethane (1mL), little magneton is added, after 90 DEG C of reaction 12h, dichloromethane (3 × 10mL) extraction is organic
Subtract each other pressure-off molten, use ethyl acetate：Petroleum ether=1:30 solvents are eluant, and 300 mesh column chromatography silica gels are filler, and column chromatography divides
From the target product (90.82mg, yield 61%) that purification is obtained.
1H NMR(500MHz,CDCl3) δ 7.72 (dd, J=7.3,1.7Hz, 2H), 7.55 (td, J=6.6,1.6Hz,
2H),5.36(s,2H),1.59(s,9H).13C NMR(125MHz,CDCl3)δ166.30,165.24,132.82,130.50,
129.66,127.99,81.46,74.54,26.94。
Claims (10)
1. the preparation method of carboxylic acid ester compound of the one kind as shown in formula (1), formula (2) or formula (3), it is characterised in that the side
Method is carried out as follows：
By aldehyde compound, tetrabutylammonium iodide, Hydrazoic acid,sodium salt, oxidant tert-butyl hydroperoxide and halogenated alkane, being dissolved in has
In machine solvent, 1～12h is reacted at 90-100 DEG C, after reaction terminates, reactant liquor is post-treated to obtain formula (1), formula (2) or formula
(3) compound shown in；The aldehyde compound, tetrabutylammonium iodide, Hydrazoic acid,sodium salt, tert-butyl hydroperoxide and halogenated alkane
Material amount ratio be 1：0.1～0.2：2～3：1.5～6：2～5；The C atoms number of described halogenated alkane is 1～5；
Wherein：In formula (1), formula (2) or formula (3), the R1For C1～4Alkyl, methoxyl group, nitro, phenyl, naphthyl, halogen or three
Methyl fluoride；The R2For C1～4The phenyl that alkyl, benzyl, phenyl or alkyl, halogen atom replace；The R3For H, methyl, ethyl or
Other chain-like alkyls；The R4For C1～4The phenyl that alkyl, benzyl, phenyl or alkyl, halogen atom replace；Described aldehydes chemical combination
Thing is the aldehyde with aromatics property.
2. the synthetic method of carboxylic acid ester compound as claimed in claim 1, it is characterised in that described aldehyde compound is：
P-methoxybenzal-dehyde, m-methoxybenzaldehyde, o-methoxybenzaldehyde, p-tolyl aldehyde, a tolyl aldehyde, adjacent methyl
Benzaldehyde, paranitrobenzaldehyde, m-nitrobenzaldehyde, 1-Formyl-2-nitrobenzene, 2- naphthaldehydes, furfural, 5- methylfuran aldehyde, 2- thiophenes
Fen formaldehyde or o-phthalaldehyde(OPA).
3. the synthetic method of carboxylic acid ester compound as claimed in claim 1, it is characterised in that described halogenated alkane is：Two
Chloromethanes, carbon tetrachloride, benzyl chloride, cylite, iodomethane, bromoethane, 1,2- dichloroethanes, n-butyl bromide, allyl chloride, bromine third
Bromide or allyl iodide.
4. the synthetic method of carboxylic acid ester compound as claimed in claim 1, it is characterised in that described organic solvent is first
Benzene, tetrahydrofuran, N,N-dimethylformamide or benzene.
5. the synthetic method of carboxylic acid ester compound as claimed in claim 1, it is characterised in that the volume of the organic solvent
Consumption is calculated as 0.2～2mL/mmol with the amount of the material of aldehyde.
6. the synthetic method of carboxylic acid ester compound as claimed in claim 1, it is characterised in that the reactant liquor post processing
Method is：After reaction terminates, reactant liquor is extracted with dichloromethane, and extract is dried vacuum removal, after solvent under reduced pressure concentration, gained
200～300 mesh silica gel of concentrate carry out column chromatography for separation, and eluant is ethyl acetate and petroleum ether volume ratio 1:20 mixing
Liquid, collects the eluent containing target compound, and concentrate drying obtains the compound shown in formula (1), formula (2) or formula (3).
7. the preparation method of carboxylic acid ester compound of the one kind as shown in formula (1), formula (2) or formula (3), it is characterised in that the side
Method is carried out as follows：
Tetrabutylammonium iodide, Hydrazoic acid,sodium salt and oxidant tert-butyl hydroperoxide are added in aldehyde compound, alkyl halide is dissolved in
In hydrocarbon, 1～12h is reacted at 90～100 DEG C, after reaction terminates, reactant liquor is post-treated to obtain formula (1), formula (2) or formula (3)
Shown compound；The amount of the material of the aldehyde compound, tetrabutylammonium iodide, Hydrazoic acid,sodium salt and tert-butyl hydroperoxide it
Than for 1：0.1～0.2：2～3：1.5～6；The C atoms number of described halogenated alkane is 1～5；
Wherein：In formula (1), formula (2) or formula (3), the R1For C1～4Alkyl, methoxyl group, nitro, phenyl, naphthyl, halogen or three
Methyl fluoride；The R2For C1～4The phenyl that alkyl, benzyl, phenyl or alkyl, halogen atom replace；The R3For H, methyl, ethyl or
Other chain-like alkyls；The R4For C1～4The phenyl that alkyl, benzyl, phenyl or alkyl, halogen atom replace；Described aldehydes chemical combination
Thing is the aldehyde with aromatics property.
8. the synthetic method of carboxylic acid ester compound as claimed in claim 7, it is characterised in that described aldehyde compound is：
P-methoxybenzal-dehyde, m-methoxybenzaldehyde, o-methoxybenzaldehyde, p-tolyl aldehyde, a tolyl aldehyde, adjacent methyl
Benzaldehyde, paranitrobenzaldehyde, m-nitrobenzaldehyde, 1-Formyl-2-nitrobenzene, 2- naphthaldehydes, furfural, 5- methylfuran aldehyde, 2- thiophenes
Fen formaldehyde or o-phthalaldehyde(OPA).
9. the synthetic method of carboxylic acid ester compound as claimed in claim 7, it is characterised in that described halogenated alkane is：Two
Chloromethanes, chloroform, carbon tetrachloride, benzyl chloride, cylite, iodomethane, bromoethane, 1,2- dichloroethanes, n-butyl bromide, allyl
Base chlorine, bromopropyl bromine or allyl iodide.
10. the synthetic method of carboxylic acid ester compound as claimed in claim 7, it is characterised in that the reactant liquor post processing
Method is：After reaction terminates, reactant liquor is extracted with dichloromethane, and extract is dried vacuum removal, after solvent under reduced pressure concentration, gained
200～300 mesh silica gel of concentrate carry out column chromatography for separation, and eluant is ethyl acetate and petroleum ether volume ratio 1:20 mixing
Liquid, collects the eluent containing target compound, and concentrate drying obtains the compound shown in formula (1), formula (2) or formula (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611006903.6A CN106588644B (en) | 2016-11-16 | 2016-11-16 | A kind of synthetic method of carboxylic acid ester compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611006903.6A CN106588644B (en) | 2016-11-16 | 2016-11-16 | A kind of synthetic method of carboxylic acid ester compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106588644A true CN106588644A (en) | 2017-04-26 |
| CN106588644B CN106588644B (en) | 2019-03-29 |
Family
ID=58590025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611006903.6A Active CN106588644B (en) | 2016-11-16 | 2016-11-16 | A kind of synthetic method of carboxylic acid ester compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106588644B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574963A (en) * | 2018-12-21 | 2019-04-05 | 厦门大学 | A kind of synthetic method of furancarboxylic acid ester type compound |
| CN115304477A (en) * | 2022-09-21 | 2022-11-08 | 湖南第一师范学院 | Preparation method of aromatic carboxylic ester |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874887A (en) * | 1987-02-13 | 1989-10-17 | Lucky, Ltd. | Process for the preparation of pyrethroid type ester compounds |
| US20020016492A1 (en) * | 2000-04-21 | 2002-02-07 | Nobuyoshi Yasuda | Process for preparing 3-hydroxymethyl-4-(aryl or heterocyclic)-cyclopentanones |
| CN1753888A (en) * | 2003-03-01 | 2006-03-29 | 阿斯利康(瑞典)有限公司 | Hydroxymethyl substituted dihydroisoxazole derivatives useful as antibiotic agents |
| CN102531956A (en) * | 2010-12-21 | 2012-07-04 | 浙江九洲药业股份有限公司 | Intermediate for preparing agomelatine and relevant preparation method |
| CN102816134A (en) * | 2012-08-03 | 2012-12-12 | 南开大学 | 1,2,3-thiadiazole-containing sulfilimine (sulfonimine) compounds and their preparation method and use |
| CN102942601A (en) * | 2012-11-30 | 2013-02-27 | 蔡进 | Method for preparing fondaparinux sodium intermediate |
| CN103596951A (en) * | 2011-04-08 | 2014-02-19 | 阿弗拉克西斯控股股份有限公司 | 8-ethyl-6-(aryl)pyrido [2,3-d]pyrimidin-7(8h)-ones for the treatment of nervous system disorders and cancer |
| CN104926646A (en) * | 2014-03-20 | 2015-09-23 | 谢阳 | Method for chemical synthesis of tanshinol and related analogues |
-
2016
- 2016-11-16 CN CN201611006903.6A patent/CN106588644B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874887A (en) * | 1987-02-13 | 1989-10-17 | Lucky, Ltd. | Process for the preparation of pyrethroid type ester compounds |
| US20020016492A1 (en) * | 2000-04-21 | 2002-02-07 | Nobuyoshi Yasuda | Process for preparing 3-hydroxymethyl-4-(aryl or heterocyclic)-cyclopentanones |
| CN1753888A (en) * | 2003-03-01 | 2006-03-29 | 阿斯利康(瑞典)有限公司 | Hydroxymethyl substituted dihydroisoxazole derivatives useful as antibiotic agents |
| CN102531956A (en) * | 2010-12-21 | 2012-07-04 | 浙江九洲药业股份有限公司 | Intermediate for preparing agomelatine and relevant preparation method |
| CN103596951A (en) * | 2011-04-08 | 2014-02-19 | 阿弗拉克西斯控股股份有限公司 | 8-ethyl-6-(aryl)pyrido [2,3-d]pyrimidin-7(8h)-ones for the treatment of nervous system disorders and cancer |
| CN102816134A (en) * | 2012-08-03 | 2012-12-12 | 南开大学 | 1,2,3-thiadiazole-containing sulfilimine (sulfonimine) compounds and their preparation method and use |
| CN102942601A (en) * | 2012-11-30 | 2013-02-27 | 蔡进 | Method for preparing fondaparinux sodium intermediate |
| CN104926646A (en) * | 2014-03-20 | 2015-09-23 | 谢阳 | Method for chemical synthesis of tanshinol and related analogues |
Non-Patent Citations (1)
| Title |
|---|
| WANG, QIAN-QIAN ET AL: "Bu4NI-catalyzed and tBuOOH-oxidized Esterification of Aldehydes with Alkyl Halides in Water", 《 ASIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574963A (en) * | 2018-12-21 | 2019-04-05 | 厦门大学 | A kind of synthetic method of furancarboxylic acid ester type compound |
| CN109574963B (en) * | 2018-12-21 | 2021-06-25 | 厦门大学 | Synthetic method of furoate compound |
| CN115304477A (en) * | 2022-09-21 | 2022-11-08 | 湖南第一师范学院 | Preparation method of aromatic carboxylic ester |
| CN115304477B (en) * | 2022-09-21 | 2024-01-26 | 湖南第一师范学院 | Preparation method of aromatic carboxylic ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106588644B (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104926811B (en) | The synthetic method of 3-cyanoimidazole also [1,2-a] pyridine compounds and application thereof | |
| CN107141207B (en) | Synthetic method of 3 '-acyl-2, 4' -dihydroxy benzophenone compound | |
| CN105801575A (en) | Synthetic method of imidazo[1,2-a]pyridine | |
| CN106588644B (en) | A kind of synthetic method of carboxylic acid ester compound | |
| CN107935812A (en) | Ruthenium is catalyzed the method that alkyl arone prepares more virtue substitution naphthalene derivativeses with tolans reaction | |
| CN109422684A (en) | A method of synthesis 6- methyl phenanthridines class compound | |
| CN105153083B (en) | Preparation method for polysubstituted furan compound | |
| CN109761897A (en) | A kind of copper catalysis N- heterocyclic arene class compound C (sp2)-H key alkylated method | |
| CN107629064B (en) | A kind of synthetic method of Azacyclooctane and Furanones compound | |
| CN107602452B (en) | Synthetic method of 3-acyl pyridine compound | |
| Kikui et al. | Iodine-mediated α-sulfonyloxylation of alkyl aryl ketones with oxone® and sulfonic acids | |
| CN106431800B (en) | (E) synthetic method of -4- oxo -2- butylene aldehyde compound | |
| CN105622625B (en) | A kind of synthetic method of benzopyrone and Imidazopyridine compound | |
| CN109734705A (en) | A method of preparation N- heterocyclic arene derivative is alkylated through dehalogenation | |
| CN106946881B (en) | A kind of amino replaces the synthetic method of naphtho- Quinolizinone type compounds | |
| CN105669667A (en) | Trifluoromethyl pyrroloquinoline derivative and synthetic method thereof | |
| CN106866654B (en) | A kind of synthetic method of naphtho- quinolizine ketone -11- amides compound | |
| CN108997365A (en) | A kind of sequential catalyst preparation method of chiral pyrazol spiral shell furfuran compound | |
| CN105237466B (en) | A kind of method for synthesizing three substituted pyridine derivatives | |
| CN108148064A (en) | A kind of method for preparing pyrazoles quinokysalines derivative | |
| CN106883241B (en) | A kind of preparation method of polysubstituted dihydrofuran [2,3-b] pyridine derivate | |
| Kirihara et al. | Synthesis of Acylsilanes via Catalytic Dedithioacetalization of 2-Silylated 1, 3-Dithianes with 30% Hydrogen Peroxide | |
| CN105693778B (en) | The method of N- methoxymethylamide guiding synthesis ferrocene and Pyridione derivatives | |
| CN110294708B (en) | Preparation method of trifluoroethylselenophenanthridine and 3, 4-dihydroisoquinoline derivatives | |
| Liu et al. | Samarium-Promoted Michael Addition between Aroyl Chlorides and Chalcones |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |