CN102241614B - A kind of synthetic method of N-alkyl-substituted amide compounds - Google Patents

A kind of synthetic method of N-alkyl-substituted amide compounds Download PDF

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Publication number
CN102241614B
CN102241614B CN201110118554.8A CN201110118554A CN102241614B CN 102241614 B CN102241614 B CN 102241614B CN 201110118554 A CN201110118554 A CN 201110118554A CN 102241614 B CN102241614 B CN 102241614B
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alkyl
amide compounds
substituted amide
immobilized
reaction
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CN102241614A (en
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周新锐
冯烈
吕爽
陈云斌
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ZHEJIANG JIANYE CHEMICAL CO Ltd
Dalian University of Technology
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ZHEJIANG JIANYE CHEMICAL CO Ltd
Dalian University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention belongs to Minute Organic Synthesis field, relate to a kind of synthetic method of N-alkyl-substituted amide compounds.It is characterized in that alkyl agent is the alkyl methyl ether with following formula: R-O-CH 3; Catalyzer has H 3pW 12o 40the phosphorus heteropoly tungstic acid under non-immobilized or immobilized condition of structure.Wherein immobilized carrier is siliceous molecular sieve, polynite or wilkinite; Amino agent is the acid amides with following formula: react solvent-free or with C 1~ C 5carboxylic acid is carry out under solvent condition, and temperature of reaction is 20 DEG C ~ 150 DEG C, and preferable range is 50 DEG C ~ 135 DEG C, and the reaction times is 2h ~ 24h, synthesis N-alkyl-substituted amide compounds.Effect of the present invention and benefit are that raw material is easy to get, reaction conditions gentle; The recyclable recycling of catalyst system, unique by-product carbinol easily reclaim and have self-value.

Description

A kind of synthetic method of N-alkyl-substituted amide compounds
Technical field
The invention belongs to Minute Organic Synthesis field, relate to a kind of synthetic method of N-alkyl-substituted amide compounds, be specifically related to the synthetic method of N-alkyl substituted sulfonamides and N-alkyl replacement carboxamide.
Technical background
N-alkyl-substituted amide compounds is important organic synthesis intermediate and fine chemical product, and be widely used in the production of the preparation of organic amine industrial chemicals, the development of new drug and conventional medicament, its corresponding synthetic method receives much concern.The conventional method of N-alkyl-substituted amide compounds is prepared in Ritter reaction, but raw material is the prussiate of severe toxicity, limit its large-scale industrial application (Sanz R, Martinez A, Guilarte V, Alvarez-Gutierrez J.M, Rodriguez F.The Ritter reaction under truly catalyticbronsted acid conditions.Eur.J.Org.Chem.2007,28,4642-4645; Ritter, J.J, Minieri, P.P.A new reaction of nitriles.I.Amides from alkenes and mononitriles.J.Am.Chem.Soc.1948,70,4045-4048.); The direct reaction of acyl chlorides and organic amine is adopted to prepare N-alkyl-substituted amide compounds method (Christian A G N Montalbetti, Virginie F.Amide bondformation and peptide coupling.Tetrahedron, 2005,61,10827-10852; Cui Tong, pays chengguang. to the derivatization reaction .1996 of phthalimidine benzene sulfonyl chloride and aminated compounds, and 13 (5), 97-99), although synthetic route is simple and direct, there is acyl chlorides and be difficult to preserve, the environmental problems such as organic amine limited source and generation HCl spent acid; Some documents (Jacques M.Palladium-catalysed reactions of alcohols.Part B:Formation of C-C and C-N bonds from unsaturated alcohols.Tetrahedron, 2005,61,4179-4212; Sreedhar B, Surendra Reddy P, Amarnath Reddy M, Neelima B, Arundhathi R.AgOTf catalyzed direct amination of benzyl alcohols withsulfonamides.Tetrahedron Lett.2007,48,8174-8177; Kenneth N.Campbell, Armiger H.Sommers, Barbara K.Campbell.Tert-Butylamide.Organic Syntheses, Coll.1955,3,148; 1947,27,12.) report with alcohols is raw material, under the precious metal such as palladium, silver or solvent of strong catalytic condition, N-alkyl-substituted amide compounds is prepared by nucleophilic substitution reaction, the method raw material economics is easy to get, but there is recovery and the Utilizing question of expensive catalyst, in a large number liquid acid.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of with alkyl methyl ether and acid amides for raw material, under Catalyzed by Phosphotungstic Acid, the novel method of direct aminatin Reactive Synthesis N-alkyl-substituted amide compounds.
The technical solution used in the present invention is:
Alkyl agent is the alkyl methyl ether with general formula (I) structure,
R-O-CH 3
(I)
(I) in formula: R=C nh 2n+1, C nh 2n-1or wherein R 1=C nh 2n+1or C nh 2n-1, the integer of n=0 ~ 12;
Catalyzer has H 3pW 12o 40the phosphorus heteropoly tungstic acid under non-immobilized or immobilized condition of structure.Wherein immobilized carrier is siliceous molecular sieve, polynite or wilkinite;
Amino agent is the acid amides with general formula (II) structure,
(II) in formula:
R 1＝C nH 2nX、 R 2＝C nH 2nX、
Wherein X=H, OH or NH 2, X 1, X 2, X 3, X 4, X 5=H, F, Br, Cl, CH 3, C 2h 5, NH 2, SO 3h or NO 2; Y=H, F, Br or Cl, the integer of n=0 ~ 12.
React solvent-free or with C 1~ C 5carboxylic acid is carry out under solvent condition, and temperature of reaction is 20 DEG C ~ 150 DEG C, and preferable range is 50 DEG C ~ 135 DEG C, and the reaction times is 2h ~ 24h, synthesis N-alkyl-substituted amide compounds.
Effect of the present invention and benefit are that raw material is easy to get, reaction conditions gentle; The recyclable recycling of catalyst system, unique by-product carbinol easily reclaim and have self-value.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.
The synthesis of embodiment 1:N-tertiary butyl para toluene sulfonamide
Take methyl tertiary butyl ether 11.1g, para toluene sulfonamide 2.14g, phospho-wolframic acid 1.0g, glacial acetic acid 15.4g; Be warming up to 60 DEG C, back flow reaction 6.5h; Stop heating, leave standstill to room temperature; Product yield 80.3%.
The synthesis of embodiment 2:4.5-bromothiophene-2-tertiary butyl sulphonamide
Take methyl tertiary butyl ether 22.2g, 5-bromothiophene-2-sulphonamide 1.0g, phospho-wolframic acid 1.0g, glacial acetic acid 15.4g; Be warming up to 55 DEG C, back flow reaction 6.5h; Stop heating, leave standstill to room temperature; Product yield 17.8%.
Embodiment 3: the synthesis taking immobilized phosphotungstic acid as catalyzer, N-tertiary butyl para toluene sulfonamide
Take 1.0g phospho-wolframic acid, add 20mL deionized water dissolving, after add 2.0g MCM-41 molecular sieve, mechanical stirring one hour, leave standstill steeped overnight; Dry at 100 DEG C except moisture, 300 DEG C of activation 4h, are cooled to room temperature, grind stand-by.
Take methyl tertiary butyl ether 11.1g, para toluene sulfonamide 2.1g, Catalyzed By Immobilized Phosphotungstic agent 3.0g, glacial acetic acid 15.4g.Be warming up to 60 DEG C, back flow reaction 6.5h; Stop heating, leave standstill to room temperature, suction filtration, filter to obtain catalyst recovery; Product yield 64.0%.
Embodiment 4: during without plus solvent, the synthesis of N-tertiary butyl para toluene sulfonamide
Take methyl tertiary butyl ether 11.1g, para toluene sulfonamide 2.1g, phospho-wolframic acid 1.0g; Be warming up to 54 DEG C, back flow reaction 6.5h; Stop heating, leave standstill to room temperature; Product yield 14.0%.
The synthesis of embodiment 5:N-t-butylbenzamide
Take methyl tertiary butyl ether 33.3g, benzamide 1.5g, phospho-wolframic acid 1.0g; Be warming up to 55 DEG C, after backflow, react 24h; Stop heating, leave standstill to room temperature; Product yield 28.6%.
The synthesis of embodiment 6:N-phenyl para toluene sulfonamide
Take methyl-phenoxide 10.8g, para toluene sulfonamide 1.7g, phospho-wolframic acid 1.0g, glacial acetic acid 20.8g; Be warming up to 70 DEG C, back flow reaction 1.5h; In 1h, be progressively warming up to 130 DEG C, period constantly steams 60 DEG C ~ 90 DEG C cuts; Stop heating, leave standstill to room temperature; Product yield 60.0%.

Claims (2)

1. a synthetic method for N-alkyl-substituted amide compounds, is characterized in that,
hydrocarbylationagent is the alkyl methyl ether with general formula (I) structure,
R-O-CH 3
(I)
(I) in formula: R=C nh 2n+1or
Wherein R 1=C nh 2n+1or C nh 2n-1, the integer of n=0 ~ 12 but n is not 0;
Catalyzer has H 3pW 12o 40structure is non- immobilized or immobilized conditionunder phosphorus heteropoly tungstic acid, wherein immobilized carrierfor siliceous molecular sieve, polynite or wilkinite;
Amino agent is the acid amides with general formula (II) structure,
(II) in formula:
Wherein X=H, OH or NH 2; X 1, X 2, X 3, X 4, X 5=H, F, Br, cl, CH 3, C 2h 5, NH 2, SO 3h or NO 2; Y=H, F, Br or cl; The integer of n=0 ~ 12;
React solvent-free or with C 1~ C 5carboxylic acid is carry out under solvent condition, and temperature of reaction is 20 DEG C ~ 150 DEG C, and the reaction times is 2h ~ 24h, synthesis N-alkyl-substituted amide compounds.
2. the synthetic method of a kind of N-alkyl-substituted amide compounds according to claim 1, is characterized in that, temperature of reaction is 50 DEG C ~ 135 DEG C.
CN201110118554.8A 2011-05-10 2011-05-10 A kind of synthetic method of N-alkyl-substituted amide compounds Active CN102241614B (en)

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CN103819369B (en) * 2014-03-11 2016-06-01 杨雪飞 The synthetic method of a kind of benzenesulfonamides

Citations (1)

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Publication number Priority date Publication date Assignee Title
US20090221820A1 (en) * 2007-12-12 2009-09-03 Massachusetts Institute Of Technology Ligands for Transition-Metal-Catalyzed Cross-Couplings, and Methods of Use Thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090221820A1 (en) * 2007-12-12 2009-09-03 Massachusetts Institute Of Technology Ligands for Transition-Metal-Catalyzed Cross-Couplings, and Methods of Use Thereof

Non-Patent Citations (5)

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Title
"An efficient FeCl3-catalyzed amidation reaction of secondary benzylic and allylic alcohols with carboxamides or p-toluenesulfonamide";Umasish Jana等;《Tetrahedron Letters》;20080128;第49卷(第5期);第858-861页 *
"N-Alkylation of Amides. A Novel Procedure";HERBERTE . JOHNS等;《Journal of Organic Chemistry》;19620630;第27卷(第6期);第2205页 *
"Phosphotungstic Acid Catalyzed Amidation of Alcohols";Wang Guan-Wu等;《Eur. J. Org. Chem.》;20080717;第2008卷(第25期);第4367-4370页 *
"Simple and Versatile Catalytic System for N-Alkylation of Sulfonamides with Various Alcohols";Zhu Mingwen等;《Organic Letters》;20100225;第12卷(第6期);第1336-1339页 *
"TiCl4-promoted direct N-acylation of sulfonamide with carboxylic ester";Fu Shaomin等;《Tetrahedron Letters》;20100906;第51卷(第44期);第5834-5837页 *

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