CN106810444A - A kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester - Google Patents

A kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester Download PDF

Info

Publication number
CN106810444A
CN106810444A CN201510869300.8A CN201510869300A CN106810444A CN 106810444 A CN106810444 A CN 106810444A CN 201510869300 A CN201510869300 A CN 201510869300A CN 106810444 A CN106810444 A CN 106810444A
Authority
CN
China
Prior art keywords
carbonate
halogenated alkane
reaction
dmap
chlorobenzoyl chloride
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
Application number
CN201510869300.8A
Other languages
Chinese (zh)
Other versions
CN106810444B (en
Inventor
高爽
任兰会
王连月
吕迎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Kate Polytron Technologies Inc
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201510869300.8A priority Critical patent/CN106810444B/en
Publication of CN106810444A publication Critical patent/CN106810444A/en
Application granted granted Critical
Publication of CN106810444B publication Critical patent/CN106810444B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of chlorobenzoyl chloride and the method for halogenated alkane reaction generation ester, with chlorobenzoyl chloride, halogenated alkane, carbonate as reaction substrate, DMAP (DMAP) is catalyst, so that in air or atmosphere of inert gases, heating, stirring reaction obtain corresponding ester products.Preparation method of the invention is first reaction substrate using chlorobenzoyl chloride, halogenated alkane, carbonate, is found that carbonate is the source of the oxygen in product first, finds that the reaction is free radical mechanism first.

Description

A kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester
Technical field
The present invention relates to a kind of chlorobenzoyl chloride and the method for halogenated alkane reaction generation ester, and in particular to a kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester.
Background technology
Esterification is an important reaction in organic chemistry.Ester type compound is also widely used for the synthesis of various fine chemicals.Traditional esterification uses carboxylic acid derivates and alcohol as reaction substrate.This kind of reaction is used as classical reaction write-in organic chemistry textbooks, such as acyl chlorides and correspondent alcohol reaction generation ester, or ester and other alcohol reaction generation ester.So far, in the presence of carbonate and DMAP (DMAP), chlorobenzoyl chloride and halogenated alkane reaction generation ester have not been reported.
The content of the invention
The invention discloses a kind of chlorobenzoyl chloride and the method for halogenated alkane reaction generation ester, with chlorobenzoyl chloride, halogenated alkane, carbonate as reaction substrate, DMAP (DMAP) is catalyst, with air or atmosphere of inert gases, heating response, obtains corresponding ester products.Preparation method of the invention is first reaction substrate using chlorobenzoyl chloride, halogenated alkane, carbonate, is found that carbonate is the source of the oxygen in product first, finds that the reaction is free radical mechanism first.
In above-mentioned technical proposal, oxygen derives from carbonate in product ester.
In above-mentioned technical proposal, reaction temperature is 50-100 DEG C, and the reaction time is 12-48h.
In above-mentioned technical proposal, described halogenated alkane is (2- chloroethyls) benzene, Isosorbide-5-Nitrae-dichloroetane, 3- chloropropyls benzene, 4- chlorobutyronitriles, benzyl chloride, 1- chlorine but-2-ene, the chloro- 2- Ethyl Methyl Ethers of 1-.
In above-mentioned technical proposal, described carbonate is cesium carbonate, potassium carbonate, sodium carbonate, lithium carbonate.
In above-mentioned technical proposal, described inert gas is argon gas, nitrogen.
In above-mentioned technical proposal, chlorobenzoyl chloride, halogenated alkane, the mol ratio of carbonate are 1:5:0.75.
In above-mentioned technical proposal, consumption and the chlorobenzoyl chloride mol ratio of DMAP (DMAP) are 2:100~10:100.
Because such scheme is used, the present invention has following advantages compared with prior art：
1. present invention employs have no document report with benzene first, halogenated alkane, carbonate reaction substrate, DMAP (DMAP) is catalyst, the method for preparing corresponding ester products.
2. present invention firstly discovers that carbonate is the source of the oxygen in product.
3. present invention firstly discovers that the reaction is free radical mechanism.
4. reaction yield reaches as high as 90%.
Specific embodiment
With reference to embodiment in detail the present invention is described in detail, but the scope of the invention is not limited to following embodiments.
The method of chlorobenzoyl chloride and halogenated alkane reaction generation ester：
The synthesis of phenylethyl benzoic ether
0.5mmol chlorobenzoyl chlorides, 0.35mmol Cs are sequentially added in the reaction tube of 35mL2CO3, 2mol%DMAP, 2.5mmol (2- chloroethyls) benzene.After reaction system stirs 24h at 50 DEG C, column chromatography treatment (ethyl acetate/n-hexane=1:50-1:10).The yield of phenylethyl benzoic ether is 87% (98.4mg).Water white oil.1H NMR(400MHz,CDCl3)δppm:7.97-7.84 (m, 2H), 7.41 (t, J=7.4Hz, 1H), 7.29 (t, J=7.7Hz, 2H), 7.23-7.07 (m, 5H), 4.41 (t, J=7.0Hz, 2H), 2.95 (t, J=7.0Hz, 2H)；13C NMR(101MHz,CDCl3)δppm:166.55,137.99,132.97,130.38,129.64,129.04,128.62,128.42,126.67,65.54,35.32.HRMS(ESI)for C15H14O2,calcd:226.0994,found:226.0991.
4- chlorobutyl benzoic ethers
0.5mmol chlorobenzoyl chlorides, 0.5mmol Cs are sequentially added in the reaction tube of 35mL2CO3, 5mol%DMAP, 2.5mmol Isosorbide-5-Nitrae-dichloroetane.After reaction system stirs 24h at 50 DEG C, column chromatography treatment (ethyl acetate/n-hexane=1:50-1:10).Yield 89% (94.7mg).Yellow oil；1H NMR(400MHz,CDCl3)δppm:8.13-7.98 (m, 2H), 7.55 (t, J=7.4Hz, 1H), 7.44 (t, J=7.7Hz, 2H), 4.43-4.28 (m, 2H), 3.67-3.54 (m, 2H), 2.03-1.86 (m, 4H)；13C NMR(101MHz,CDCl3)δppm:166.53,132.98130.23,129.55,128.40,64.11,44.52,29.28,26.19.HRMS(ESI)for C11H13ClO2,calcd:212.0604,found:212.0599.
3- phenyl propyl benzoic ethers
0.5mmol chlorobenzoyl chlorides, 0.5mmol Cs are sequentially added in the reaction tube of 35mL2CO3, 5mol%DMAP, 3.5mmol 3- chloropropyl benzene.After reaction system stirs 12h at 100 DEG C, column chromatography treatment (ethyl acetate/n-hexane=1:50-1:10).Yield 81% (97.3mg).Water white oil；1H NMR(400MHz,CDCl3)δppm:8.03 (dd, J=5.2,2.8Hz, 2H), 7.57-7.46 (m, 1H), 7.40 (t, J=7.7Hz, 2H), 7.31-7.11 (m, 5H), 4.32 (t, J=6.5Hz, 2H), 2.76 (t, J=7.6Hz, 2H), 2.13-2.00 (m, 2H)；13C NMR(101MHz,CDCl3)δppm:166.62,141.26,132.95,130.48,129.64,128.66-128.33(m),126.12,64.33,32.39,30.39.HRMS(ESI)for C16H16O2,calcd:240.1150,found:240.1151.
3- cyanopropyl benzoic ethers
0.5mmol chlorobenzoyl chlorides, 0.3mmol Cs are sequentially added in the reaction tube of 35mL2CO3, 3mol%DMAP, 2.5mmol 4- butyronitrile.After reaction system stirs 16h at 70 DEG C, column chromatography treatment (ethyl acetate/n-hexane=1:50-1:10).Yield 82% (77.6mg).Yellow oil；1H NMR(400MHz,CDCl3)δppm:8.12-7.95 (m, 2H), 7.63-7.50 (m, 1H), 7.45 (dd, J=9.0,4.2Hz, 2H), 4.43 (td, J=6.2,2.6Hz, 2H), 2.63-2.45 (m, 2H), 2.14 (dd, J=8.3,3.6Hz, 2H)；13C NMR(101MHz,CDCl3)δppm:(d, J=5.1Hz), 166.28,133.28,129.66 128.50,118.95,78.14-77.70 (m), 62.74,25.03,14.46.HRMS (ESI) for C11H11NO2,calcd:189.0790,found:189.0788.
Ergol
0.5mmol chlorobenzoyl chlorides, 0.3mmol Cs are sequentially added in the reaction tube of 35mL2CO3, 5mol%DMAP, 3mmol benzyl chloride.After reaction system stirs 16h at 80 DEG C, column chromatography treatment (ethyl acetate/n-hexane=1:50-1:10).Yield 82% (77.6mg).Yield 86% (91.3mg).Yellow oil；1H NMR(400MHz,CDCl3)δppm:8.00-7.91(m,2H),7.41-7.15(m,8H),5.22(s,2H)；13C NMR(101MHz,CDCl3)δppm:165.28,134.99,131.93,129.06,128.61,127.51,127.38-126.97(m),65.57.HRMS(ESI)for C14H12O2,calcd:212.0837,found:212.0836.
2- methoxy ethyl benzoic ethers
0.5mmol chlorobenzoyl chlorides, 0.3mmol Cs are sequentially added in the reaction tube of 35mL2CO3, 5mol%DMAP, 3mmol 2- chloroethyl methyl ethers.After reaction system stirs 16h at 80 DEG C, column chromatography treatment (ethyl acetate/n-hexane=1:50-1:10).Yield 90% (81.1mg).Yellow oil；1H NMR(400MHz,CDCl3)δppm:8.07 (d, J=7.4Hz, 2H), 7.55 (t, J=7.4Hz, 1H), 7.43 (t, J=7.7Hz, 2H), 4.53-4.41 (m, 2H), 3.79-3.67 (m, 2H), 3.43 (s, 3H)；13C NMR(101MHz,CDCl3)δppm:166.57,132.98,130.09,129.70,128.32,70.56,64.03,59.03.HRMS(ESI)for C10H12O3,calcd:180.0786,found:180.0788.
(E)-butyl -2- alkene -1- yl benzoic acid esters
0.5mmol chlorobenzoyl chlorides, 0.3mmol Cs are sequentially added in the reaction tube of 35mL2CO3, the chloro- 2- butylene of 5mol%DMAP, 3mmol 1-.After reaction system stirs 18h at 60 DEG C, column chromatography treatment (ethyl acetate/n-hexane=1:50-1:10).Yield 77% (67.8mg).Yellow oil；1H NMR(400MHz,CDCl3)δppm:8.03-7.86 (m, 2H), 7.41 (d, J=7.5Hz, 1H), 7.31 (t, J=7.7Hz, 2H), 5.75 (tt, J=19.4,9.7Hz, 1H), 5.68-5.49 (m, 1H), 4.71 (dd, J=55.9,6.6Hz, 2H), 1.72-1.54 (m, 3H)；13C NMR(101MHz,CDCl3)δppm:165.33,131.79,130.24,128.54,127.25,124.17,64.56,59.55,16.75.HRMS(ESI)for C11H12O2,calcd:176.0837,found:176.0835。

Claims (9)

1. a kind of method that chlorobenzoyl chloride and halogenated alkane reaction generate ester, it is characterized in that, in air or atmosphere of inert gases, using chlorobenzoyl chloride, halogenated alkane, carbonate as reaction substrate, DMAP (DMAP) is catalyst, heating, stirring reaction, product obtain ester compounds by treatment.
2. method according to claim 1, it is characterised in that described carbonate is one or more in cesium carbonate, potassium carbonate, sodium carbonate, lithium carbonate.
3. method according to claim 1, it is characterised in that the general structure of described halogenated alkane is shown below：Wherein, R is the alkyl or alkenyl that the carbon number containing substitution base is 1 to 8, and the described base containing substitution is halogen, cyano group, the alkoxy of C1-4, phenyl.
4. method according to claim 1, it is characterised in that described halogenated alkane is (2- chloroethyls) benzene, Isosorbide-5-Nitrae-dichloroetane, 3- chloropropyls benzene, 4- chlorobutyronitriles, benzyl chloride, 1- chlorine but-2-ene, the chloro- 2- Ethyl Methyl Ethers of 1-.
5. method according to claim 1, it is characterised in that described inert gas is argon gas, nitrogen.
6. method according to claim 1, it is characterised in that chlorobenzoyl chloride, halogenated alkane, the mol ratio of carbonate are 1:2:0.25-1:7:1.
7. method according to claim 2, it is characterised in that DMAP (DMAP) is 2 with chlorobenzoyl chloride mol ratio:100~10:100.
8. method according to claim 1, it is characterised in that reaction temperature is 50-100 DEG C, and the reaction time is 12-48h.
9. method according to claim 1, it is characterised in that the process step of the product is column chromatography, eluant, eluent is ethyl acetate and n-hexane, and the volume ratio of ethyl acetate and n-hexane is 1:50-1:10.
CN201510869300.8A 2015-12-01 2015-12-01 A kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester Expired - Fee Related CN106810444B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510869300.8A CN106810444B (en) 2015-12-01 2015-12-01 A kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510869300.8A CN106810444B (en) 2015-12-01 2015-12-01 A kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester

Publications (2)

Publication Number Publication Date
CN106810444A true CN106810444A (en) 2017-06-09
CN106810444B CN106810444B (en) 2018-09-04

Family

ID=59107970

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510869300.8A Expired - Fee Related CN106810444B (en) 2015-12-01 2015-12-01 A kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester

Country Status (1)

Country Link
CN (1) CN106810444B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108516935A (en) * 2018-05-21 2018-09-11 中国科学院上海有机化学研究所 A kind of perfluoro alkoxy reagent and its preparation method and application
CN112574167A (en) * 2020-12-07 2021-03-30 烟台海川化学制品有限公司 Preparation method of methylene methanedisulfonate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1218030A (en) * 1998-08-05 1999-06-02 中山市凯达精细化工股份有限公司 Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine
CN102070455A (en) * 2010-12-25 2011-05-25 温州大学 Chemical synthesis method for o-chlorobenzoic acid chloro butyl ester
CN102219818A (en) * 2011-05-05 2011-10-19 江苏省原子医学研究所 Thymidine derivates as well as preparation method and applications thereof in preparing tumor developing agents as ligand
CN102532079A (en) * 2011-12-29 2012-07-04 北京洛斯顿精细化工有限公司 Preparation method of Corey Lactone 3-benzoate
CN103664614A (en) * 2012-09-06 2014-03-26 中国石油化工股份有限公司 Preparation method of ether ester compound
JP2014210738A (en) * 2013-04-19 2014-11-13 日本テルペン化学株式会社 Dibenzyl trithiocarbonate derivative and method for producing the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1218030A (en) * 1998-08-05 1999-06-02 中山市凯达精细化工股份有限公司 Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine
CN102070455A (en) * 2010-12-25 2011-05-25 温州大学 Chemical synthesis method for o-chlorobenzoic acid chloro butyl ester
CN102219818A (en) * 2011-05-05 2011-10-19 江苏省原子医学研究所 Thymidine derivates as well as preparation method and applications thereof in preparing tumor developing agents as ligand
CN102532079A (en) * 2011-12-29 2012-07-04 北京洛斯顿精细化工有限公司 Preparation method of Corey Lactone 3-benzoate
CN103664614A (en) * 2012-09-06 2014-03-26 中国石油化工股份有限公司 Preparation method of ether ester compound
JP2014210738A (en) * 2013-04-19 2014-11-13 日本テルペン化学株式会社 Dibenzyl trithiocarbonate derivative and method for producing the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108516935A (en) * 2018-05-21 2018-09-11 中国科学院上海有机化学研究所 A kind of perfluoro alkoxy reagent and its preparation method and application
CN108516935B (en) * 2018-05-21 2021-04-20 中国科学院上海有机化学研究所 Perfluoroalkoxylation reagent and preparation method and application thereof
CN112574167A (en) * 2020-12-07 2021-03-30 烟台海川化学制品有限公司 Preparation method of methylene methanedisulfonate
CN112574167B (en) * 2020-12-07 2021-11-09 烟台海川化学制品有限公司 Preparation method of methylene methanedisulfonate

Also Published As

Publication number Publication date
CN106810444B (en) 2018-09-04

Similar Documents

Publication Publication Date Title
Wang et al. Oxalyl amide assisted palladium-catalyzed synthesis of pyrrolidones via carbonylation of γ-C (sp 3)–H bonds of aliphatic amine substrates
CN104744303B (en) Bromomethylbiphenyls of 2 R 4 ' and preparation method thereof
CN107141248A (en) A kind of method that visible light catalytic synthesizes the ketene compound of 3 sulfuryl loop coil three
Qureshi et al. Introduction of hindered electrophiles via C–H functionalization in a palladium-catalyzed multicomponent domino reaction
CN106187858A (en) A kind of synthetic method of β iodine N alkoxyamine compounds
CN106810444B (en) A kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester
KR101529403B1 (en) 3,4-dialkylbiphenyldicarboxylic acid compound, 3,4-dicarboalkoxybiphenyl-3',4'-dicarboxylic acid and corresponding acid anhydrides, and processes for producing these compounds
Jin et al. A Green Synthetic Route to Imides from Terminal Alkynes and Amides by Simple Solid Catalysts
CN104151214A (en) Method for synthesizing 2-sulfonyl ketone compounds
Jiang et al. Copper‐Catalyzed Decarboxylative Methylation of Aromatic Carboxylic Acids with PhI (OAc) 2
JP5963140B2 (en) Asymmetric dehydration condensation agent
CN109134320B (en) Synthesis method of beta-hydroxyl substituted sulfonyl compound
CN106810411B (en) A kind of method of acyl chlorides and 1,2- dichloroethanes reaction generation ester
CN106397377B (en) The method of fluorine on a kind of electron rich five-ring heterocycles acid and its derivative decarboxylation
CN112321475B (en) Gamma-amino acid analogue and synthetic method thereof
CN109503468B (en) Activation method of perfluoroalkyl carbon halogen bond and method for synthesizing pyridine derivative
Thorat et al. An efficient route for the allylation of arylaldehydes to give enantiopure homoallylic alcohols
CN108658835B (en) Method for synthesizing indole-2-ketone compound
EP2922813A1 (en) Hydrocarbonylation or methoxycarbonylation of 1,3-diene derivatives with palladium complex
Sugiyama et al. The first example of γ-chloromagnesio γ-lactones: their generation from γ-tolylsulfinyl γ-lactones with isopropylmagnesium chloride, stability, and reaction with electrophiles
US9809514B2 (en) Method for producing (bromomethyl)cyclopropane and (bromomethyl)cyclobutane
CN108409630B (en) Preparation method of 3-hydroxy-2-indolone derivative in aqueous phase
CN105646119B (en) A kind of method of fluorine in cinnamic acid and its derivative decarboxylation
CN1224419A (en) Process for preparing 1-alkyl-4-(2-chloro-3-alkoxy-4-alkylsulfonylbenzoyl)-5-hydroxypyrazole and related compounds
CN108623503A (en) A kind of environment-friendly preparation method thereof of water phase medium vinyl sulfone derivative

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
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20190521

Address after: 266000 701 households on the 7th floor of No. 3 Building of Yanguitang, 17 Kunshan Road, North District of Qingdao City, Shandong Province

Patentee after: Shandong Kate Polytron Technologies Inc

Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian

Patentee before: Dalian Institute of Chemical Physics, Chinese Academy of Sciences

CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180904

Termination date: 20201201