CN106045870B - A kind of method for preparing amide - Google Patents
A kind of method for preparing amide Download PDFInfo
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- CN106045870B CN106045870B CN201610528425.9A CN201610528425A CN106045870B CN 106045870 B CN106045870 B CN 106045870B CN 201610528425 A CN201610528425 A CN 201610528425A CN 106045870 B CN106045870 B CN 106045870B
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- reaction
- organic
- phosphine oxide
- amide
- amine
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- 150000001408 amides Chemical class 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 12
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 230000003213 activating effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000005311 nuclear magnetism Effects 0.000 description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 13
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 3
- 238000011938 amidation process Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- -1 Phosphine compound Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- ZVSKZLHKADLHSD-UHFFFAOYSA-N benzanilide Chemical compound C=1C=CC=CC=1C(=O)NC1=CC=CC=C1 ZVSKZLHKADLHSD-UHFFFAOYSA-N 0.000 description 1
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSUTZIPSLNPTAU-UHFFFAOYSA-N n-benzyl-4-nitrobenzamide Chemical class C1=CC([N+](=O)[O-])=CC=C1C(=O)NCC1=CC=CC=C1 WSUTZIPSLNPTAU-UHFFFAOYSA-N 0.000 description 1
- LKQUCICFTHBFAL-UHFFFAOYSA-N n-benzylbenzamide Chemical class C=1C=CC=CC=1C(=O)NCC1=CC=CC=C1 LKQUCICFTHBFAL-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of method for preparing amide, triphen phosphine oxide, oxalyl chloride, organic acid and organic amine are weighed according to molar ratio, triphen phosphine oxide, oxalyl chloride, organic acid and organic amine molar ratio be 1 ~ 5:1~5:1:0.3~4；Above-mentioned material is added in a reaction vessel, in N2Stirring under environment, reaction temperature are 10 40 DEG C, the reaction time is the reaction of 0.5 5 hours, in the presence of an organic organic acid and organic amine, generate corresponding amide.The present invention promotes the synthesis of amide using triphen phosphine oxide as novel carboxylic acid activating agent, and method reaction temperature of the invention is low, the reaction time is short, carboxylic acid activating agent's triphen phosphine oxide is cheap and easy to get, and recyclable recycling, byproduct of reaction only have CO and CO2, there is higher atom utilization.
Description
Technical field：
The invention belongs to organic chemistry fileds, are related to a kind of amide, specifically a kind of method for preparing amide.
Background technology：
Amido bond is one of most important chemical functional group in nature, is the main composition portion of biological vivo protein
Point, it is widely present in natural products, pesticide and pharmaceutical molecules.By market survey, in about 25% well selling medicine molecule all
Contain amido bond.Just because of the extensive use of amido bond, it is of great significance to the research of its synthetic method.Traditional amide bond
The carboxylic acid for being synthesized by a molecule and the amine of a molecule directly react, while generate the water of a molecule.But the method is anti-
Answer that temperature is high, conversion ratio is low, purification difficult.
To avoid the above problem, the synthesis of amido bond generally adds in coupling agent or substituting agent by carboxylic acid elder generation in the reaction system
The carboxylic acid derivates such as corresponding acid anhydrides or acyl chlorides are converted into, then carry out the amination of next step.This method reaction condition is mild, production
Rate is high.Phosphine compound can also be used as amide and react effective coupling agent or catalyst, spread out including various phosphines or phosphoric acid
Biology, P (OEt)3、POCl3、T3P、PPh3Deng.Amidation process wherein by the use of triphenylphosphine as coupling agent causes our note
Meaning.1966, Lee et al. had found PPh3And CCl4Amidation process can be effectively catalyzed.By further investigation revealed that PPh3
The progress of amidation process, such as CCl can also be promoted with other halogenating agents3CN、I2、NBS、Br2、BrCCl3、CBr4.This
The mechanism reacted a bit is similar, is all PPh3It reacts to form a kind of phosphonium salt with halogenating agent, activator of this phosphonium salt as carboxylic acid,
So as to promote the progress of reaction.But after the completion of reaction, it is transformed triphen phosphine oxide by triphenylphosphine, not only makes the pure of product
Change becomes Atom economy that is difficult, while being greatly reduced reaction.Although Mecinovi ' c seminars pass through in the reaction
The method of in-situ reducing triphen phosphine oxide overcomes this defect, but complicated reaction system considerably increases the cost of reaction.
In addition to this, the coupling agent of the stoichiometry added in reaction process can generate the by-product of equivalent, so as to cause reaction later
Atom utilization be remarkably decreased.
Invention content：
For above-mentioned technical problem of the prior art, the present invention provides a kind of method for preparing amide, described this
The method that kind prepares amide will solve of high cost, the severe reaction conditions of synthesizing amide key in the prior art, low yield, and purifying is stranded
The technical issues of difficult.
The present invention provides a kind of methods for preparing amide, include the following steps：
1) triphen phosphine oxide, oxalyl chloride, organic acid and organic amine, triphen phosphine oxide, oxalyl chloride, organic acid are weighed according to molar ratio
Molar ratio with organic amine is 1~5:1~5:1:0.3~4；
2) above-mentioned material is added in a reaction vessel, in N2It is stirred under environment, reaction temperature is 10-40 DEG C, anti-
It is the reaction of 0.5-5 hours, in the presence of an organic organic acid and organic amine between seasonable, generates corresponding amide.
Further, the organic acid is any one in aromatic acid, aliphatic acid.
Further, the organic amine is any one in aromatic amine, fatty amine.
Further, the organic solvent is any one in acetonitrile, dichloromethane, toluene or 1,2- dichloroethanes
Kind.
Further, extent of reaction is tracked using TLC in reaction process, determines optimum reacting time.It uses after reaction
Column chromatography is quantified, and is carried out with nuclear-magnetism qualitative.
Preferably, the molar ratio of triphen phosphine oxide, oxalyl chloride, organic acid and organic amine is 1:1:1:1.
The equation that the present invention reacts is as follows：
It is compared with the method for conventional synthesis amide, the present invention promotes acyl using triphen phosphine oxide as novel carboxylic acid activating agent
The synthesis of amine, the method high conversion rate of the synthesizing amide key provided, reaction condition is mild, the reaction time is short.
It is of the invention with it is general by activating carboxy acid promote amide synthetic method compared with, activator used in the present invention
Triphen phosphine oxide is cheap and easy to get, and recyclable recycling after the completion of reaction, the by-product of reaction system only have CO and CO2,
With higher atom utilization.It is used in the present invention compared with triphenylphosphine is as the method for the synthesizing amide of coupling agent
Coupling agent triphen phosphine oxide substantially reduces reaction cost, and the Atom economy of reaction significantly improves.With triphenylphosphine as catalysis
Agent, the method for in-situ reducing triphen phosphine oxide are compared, and method reaction system provided by the present invention is simpler, and the reaction time is more
It is short.
The present invention is compared with prior art, and technological progress is significant.The present invention provides a kind of novel, environment friends
Good, efficiently to prepare amide method, method reaction temperature of the invention is low, the reaction time is short.
Description of the drawings
Fig. 1 is the nuclear-magnetism figure of embodiment 1.
Fig. 2 is the nuclear-magnetism figure of embodiment 2.
Fig. 3 is the nuclear-magnetism figure of embodiment 3.
Fig. 4 is the nuclear-magnetism figure of embodiment 4.
Specific embodiment：
The technology of the present invention is described further below by specific embodiment and with reference to attached drawing, but the protection model of the present invention
It encloses and is not limited to following embodiments.
Embodiment 1：
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flasks, vacuumizes logical N2, the acetonitrile of 5mL is added in, magnetic force stirs
The oxalyl chloride that 0.55mL is slowly added dropwise is mixed down, reaction is violent at this time, releases a large amount of gas, reacts 10 minutes.Then it adds in
The benzoic acid of 0.61g and the aniline of 0.59mL react 0.5 hour, react and tracked with TLC, determined with column chromatography at room temperature
Amount, is carried out qualitative with nuclear-magnetism.The yield of benzanilide is 94%, and nuclear-magnetism figure is shown in attached drawing 1.
Embodiment 2：
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flasks, vacuumizes logical N2, add in the acetonitrile of 5mL, magnetic agitation
Under the oxalyl chloride of 0.55mL is slowly added dropwise, reaction is violent at this time, releases a large amount of gas, reacts 10 minutes.Then 0.61g is added in
Benzoic acid and 0.71mL benzylamine, react 0.5 hour at room temperature, react and tracked with TLC, it is fixed with column chromatography purify
Amount, the yields of N- benzyl benzamides are 91%, are carried out with nuclear-magnetism qualitative, and nuclear-magnetism figure is shown in attached drawing 2.
Embodiment 3：
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flasks, vacuumizes logical N2, add in the acetonitrile of 5mL, magnetic agitation
Under the oxalyl chloride of 0.55mL is slowly added dropwise, reaction is violent at this time, releases a large amount of gas, reacts 10 minutes.Then 0.86g is added in
α-naphthoicacid and 0.71mL benzylamine, react 0.5 hour at room temperature, react and tracked with TLC, it is fixed with column chromatography purify
Amount, the yield of N- benzyl-alphas-naphthalenecarboxamide are 75%, are carried out with nuclear-magnetism qualitative, and nuclear-magnetism figure is shown in attached drawing 3.
Embodiment 4：
The triphen phosphine oxide of 1.40g is added in 100mL three-necked flasks, vacuumizes logical N2, add in the acetonitrile of 5mL, magnetic agitation
Under the oxalyl chloride of 0.55mL is slowly added dropwise, reaction is violent at this time, releases a large amount of gas, reacts 10 minutes.Then 0.84g is added in
Paranitrobenzoic acid and 0.71mL benzylamine, at room temperature react 0.5 hour, react and tracked with TLC, carried with column chromatography
Pure quantitative, the yields of N- benzyl -4- nitrobenzamides is 81%, is carried out with nuclear-magnetism qualitative, and nuclear-magnetism figure is shown in attached drawing 4.
Claims (2)
- A kind of 1. method for preparing amide, it is characterised in that include the following steps：1）According to mole weighing triphen phosphine oxide, oxalyl chloride, organic acid and organic amine, triphen phosphine oxide, oxalyl chloride, organic acid and organic The molar ratio of amine is 1 ~ 5:1~5:1:0.3~4；The organic acid is any one in aromatic acid, aliphatic acid, the organic amine It is any one in aromatic amine, fatty amine；2）Above-mentioned material is added in a reaction vessel, in N2Stirring, reaction temperature are 10-40 DEG C, reaction time under environment It is the reaction of 0.5-5 hours, in the presence of an organic organic acid and organic amine, generates corresponding amide, the organic solvent is Any one in acetonitrile, dichloromethane, toluene or 1,2- dichloroethanes.
- 2. a kind of method for preparing amide according to claim 1, it is characterised in that：It is tracked in reaction process using TLC Extent of reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610528425.9A CN106045870B (en) | 2016-07-07 | 2016-07-07 | A kind of method for preparing amide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610528425.9A CN106045870B (en) | 2016-07-07 | 2016-07-07 | A kind of method for preparing amide |
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| Publication Number | Publication Date |
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| CN106045870A CN106045870A (en) | 2016-10-26 |
| CN106045870B true CN106045870B (en) | 2018-07-03 |
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| CN201610528425.9A Expired - Fee Related CN106045870B (en) | 2016-07-07 | 2016-07-07 | A kind of method for preparing amide |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111514150B (en) * | 2020-05-22 | 2021-12-28 | 清华大学 | Application of TPPO in inhibiting FPP-induced cell death and corresponding reperfusion injury |
| CN113336671A (en) * | 2021-04-28 | 2021-09-03 | 宁波大学 | Preparation method of amide or ester compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005063018A1 (en) * | 2003-12-25 | 2005-07-14 | Ishihara Sangyo Kaisha, Ltd. | Haloalkene compounds, process for their production and pesticides containing them |
| CN104058983A (en) * | 2014-07-02 | 2014-09-24 | 郑攀锋 | Method for synthesizing medicine raw material amide compounds |
| CN104245666A (en) * | 2012-02-07 | 2014-12-24 | 拜耳知识产权有限责任公司 | Method for producing substituted anthranilic acid derivatives |
| CN105330532A (en) * | 2015-12-14 | 2016-02-17 | 山东凯盛新材料有限公司 | Preparation method of p-Methyl benzoyl chloride |
-
2016
- 2016-07-07 CN CN201610528425.9A patent/CN106045870B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005063018A1 (en) * | 2003-12-25 | 2005-07-14 | Ishihara Sangyo Kaisha, Ltd. | Haloalkene compounds, process for their production and pesticides containing them |
| CN104245666A (en) * | 2012-02-07 | 2014-12-24 | 拜耳知识产权有限责任公司 | Method for producing substituted anthranilic acid derivatives |
| CN104058983A (en) * | 2014-07-02 | 2014-09-24 | 郑攀锋 | Method for synthesizing medicine raw material amide compounds |
| CN105330532A (en) * | 2015-12-14 | 2016-02-17 | 山东凯盛新材料有限公司 | Preparation method of p-Methyl benzoyl chloride |
Non-Patent Citations (2)
| Title |
|---|
| A comparative study of two different methods for direct polyamidation of N-trimellitylimido-L-methionine with various aromatic diamines;Shadpour Mallakpour，Majid Kolahdoozan;《Designed Monomers and Polymers》;20120402;第10卷(第5期);第439–448页 * |
| A procedure for Appel halogenations and dehydrations using a polystyrene supported phosphine oxide;Xiaoping Tang等;《Tetrahedron Letters》;20131202;第55卷;第799-802页 * |
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