CN108689880A - Solventless method prepares diphenyl hydroxypropionitrile - Google Patents
Solventless method prepares diphenyl hydroxypropionitrile Download PDFInfo
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- CN108689880A CN108689880A CN201810780716.6A CN201810780716A CN108689880A CN 108689880 A CN108689880 A CN 108689880A CN 201810780716 A CN201810780716 A CN 201810780716A CN 108689880 A CN108689880 A CN 108689880A
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- CN
- China
- Prior art keywords
- diphenyl
- reaction
- hydroxypropionitriles
- dosage
- samarium
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- 238000000034 method Methods 0.000 title claims abstract description 19
- YMDXFHNZIJDMTI-UHFFFAOYSA-N 2-hydroxy-2,3-diphenylpropanenitrile Chemical compound C=1C=CC=CC=1C(O)(C#N)CC1=CC=CC=C1 YMDXFHNZIJDMTI-UHFFFAOYSA-N 0.000 title description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012965 benzophenone Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 11
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 11
- 239000004305 biphenyl Substances 0.000 claims abstract description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 9
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011541 reaction mixture Substances 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- -1 acetonitrile Nitrile Chemical class 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- OSGUMQGPGBZSGN-UHFFFAOYSA-N 3-hydroxy-3,3-diphenylpropanenitrile Chemical compound C=1C=CC=CC=1C(CC#N)(O)C1=CC=CC=C1 OSGUMQGPGBZSGN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000010992 reflux Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000012043 crude product Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VFOKYTYWXOYPOX-RVDMUPIBSA-N (z)-2,3-diphenylprop-2-enenitrile Chemical compound C=1C=CC=CC=1C(/C#N)=C/C1=CC=CC=C1 VFOKYTYWXOYPOX-RVDMUPIBSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical group ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- WOFDVDFSGLBFAC-UHFFFAOYSA-N lactonitrile Chemical compound CC(O)C#N WOFDVDFSGLBFAC-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
Abstract
The invention discloses a kind of to promote benzophenone and the acetonitrile method that coupling reaction prepares 3,3- diphenyl -3- hydroxypropionitriles under solvent-free conditions under cuprous iodide catalysis using samarium metal.Under stirring by benzophenone in a small amount of acetonitrile mixed dissolution, then sequentially add samarium metal powder, catalytic amount iodine, catalytic amount cuprous iodide powder.Reaction system carries out under the conditions of anhydrous.Reaction temperature can be room temperature or reflux.Under stirring until the reaction is complete.Obtained reaction mixture is post-treated to obtain crude product, obtains 3,3- diphenyl -3- hydroxypropionitriles through pillar layer separation, recrystallizes to obtain sterling, yield 90-99%.
Description
Technical field
The invention belongs to organic chemical synthesis fields, and in particular to a kind of system promoted under solvent-free conditions with samarium metal
The method of standby diphenyl hydroxypropionitrile.
Background technology
Diphenyl hydroxypropionitrile full name is 3,3- diphenyl -3- hydroxypropionitriles, and chemical constitution is as follows:
Diphenyl hydroxypropionitrile often can be used for because having cyano, hydroxy functional group simultaneously at 1,3- in its molecular structure
Synthesize the nitrogen-containing hetero cyclics with multiple biological activities;Document 1.Itami, Kenichiro et al, PCT
Int.Appl., 2014122811,2014. document 2.Meng, Lingkui et al, Angewandte Chemie,
International Edition,52(38),10048-10051;2013];In addition, diphenyl hydroxypropionitrile class compound can
To generate diphenyl acrylonitrile by hydroxyl elimination reaction, cyano can also generate carboxylic acid by hydrolysis or be reduced to amine chemical combination
Object, its these derivatives are all widely used organic synthesis intermediates.The synthetic method of diphenyl hydroxypropionitrile class compound
Relatively simple, generally relatively common is prepared by condensation reaction using benzophenone and acetonitrile.But, this kind of synthesis side
Method generally requires to use the not easy-operating reagent such as excessive butyl lithium, LDA, KOH, and exist more reaction route it is tediously long, reaction
Condition harshness, low yield Deng Wenti [Document 3.Arseniyadis, Simeon et al, Organic Reactions
(Hoboken,NJ,United States),31;1984].These problems may cause serious environment in extensive prepare
Problem.
Traditional chemical reacts and its relevant chemical industry is main source that the world today seriously pollutes, pollution it is very big
Part comes from a large amount of effumability organic solvent used in reaction process, such as benzene, chloralkane, alcohol, ketone, ethers.
For the pollution of organic solvent, it is important research content to find green alternative.Wherein, solvent-free organic reaction is current
A kind of important method in green substitute technology.
The invention discloses one kind in a small amount of acetonitrile, cuprous iodide catalysis it is lower using samarium metal promote diphenylmethanone and
The method that coupling reaction prepares diphenyl hydroxypropionitrile occurs for acetonitrile, and this method is there is not yet domestic and foreign literature is reported.
Invention content
The purpose of the present invention is to provide diphenylmethanone under a kind of condition of no solvent and acetonitrile simple and regular reaction
Under the conditions of coupling prepare the short-cut method of diphenyl hydroxypropionitrile.
Technical scheme is as follows:
In the presence of the iodine of catalytic amount, catalytic amount cuprous iodide, benzophenone and acetonitrile are directly coupled using samarium metal
For diphenyl hydroxypropionitrile, reaction formula is shown below:
Specific technical solution is:Under stirring by benzophenone in a small amount of acetonitrile mixed dissolution, then sequentially add metal
Samarium powder, iodine, cuprous iodide powder.Wherein, acetonitrile content is 1-3 times of the mass ratio of benzophenone dosage;Samarium powder dosage is hexichol
0.1-0.5 times of the molar ratio of ketone dosage;The dosage of iodine is 0.01-0.05 times of the molar ratio of samarium powder dosage;Cuprous iodide dosage
For 0.01-0.05 times of the molar ratio of samarium powder dosage;Reaction system carries out under the conditions of anhydrous.Range of reaction temperature can be room
Temperature arrives reflux temperature.
Under stirring until the reaction is complete.After obtained reaction mixture is post-treated, the isolated diphenyl of chromatographic column
Hydroxypropionitrile sterling, yield 90-99%.
The advantages and positive effects of the present invention:
Synthetic route of the present invention is simple and efficient, and diphenyl hydroxypropionitrile, operation step need to be only can be obtained by single step reaction
It is rapid few, it avoids using a large amount of highly basic, is not necessarily to separation of intermediates, last handling process is simple, and product is easily isolated, and greatly simplifies
Operation requires;Reaction condition of the present invention is easily achieved, and does not need harsh conditions such as low temperature, high temperature, illumination, pressure, strong acid and strong base
Etc. conditions, avoid the particular/special requirements such as living things catalysis, precious metal catalyst;Samarium metal used shows excellent reaction in the present invention
Property, making benzophenone, smoothly coupling is diphenyl hydroxypropionitrile with acetonitrile, other metals such as magnesium metal, zinc are similar in contrast
Under the conditions of be difficult to realize such conversion, due to samarium be rare earth metal, the rare earth resources in China account for 90% of the world or more, therefore have
Effect develops and uses rare earth metal and is of great significance to China;It is directly reacted with a small amount of acetonitrile in the present invention, avoiding makes
With other solvents, this had both made greenization technical process, and thus reaction cost was made further to decline, and improved reaction system
Concentration to intensified response effect.
Specific implementation mode
Following synthesis example is used for further illustrating the present invention, but is not intended to limit the present invention.
Example 1
3.6g benzophenone, 4.1mL are sequentially added into dry reaction vessel and removes water dry acetonitrile in advance, and stirring is molten
Xie Hou continuously adds the samarium metal powder, 5mg iodine and 2.6mg cuprous iodides of 0.9g brand-news, magnetic agitation.Reaction is in gentle reflux
It is carried out under state, reacts 0.5h.Reaction solution is extracted with ethyl acetate, post-treated to obtain diphenyl hydroxypropionitrile crude product.Then
Further pillar layer separation and by recrystallization purifying, obtains diphenyl hydroxypropionitrile, yield 92%.
3- hydroxyl -3,3- diphenyl propionitrile, white solid, 141-142 DEG C of of fusing point1HNMR(500MHz,CDCl3)δppm
2.67-2.71(s,1H),3.24-3.28(s,2H),7.14-7.43(m,9H).
Example 2
By 1 method of example, using the samarium powder of 1.5g brand-news, other conditions are constant, obtain diphenyl hydroxypropionitrile, yield
97%.
Example 3
By 1 method of example, reaction temperature is room temperature condition, and other conditions are constant, obtains diphenyl hydroxypropionitrile, yield
73%.
Claims (6)
1. a kind of method of synthesis 3,3- diphenyl -3- hydroxypropionitriles, it is characterised in that under a small amount of iodine and cuprous iodide catalysis,
Benzophenone and one step coupling reaction of acetonitrile is promoted to prepare 3,3- diphenyl -3- hydroxyls third using samarium metal in a small amount of acetonitrile
Nitrile, preparation process include the following steps:
Under stirring by benzophenone in acetonitrile mixed dissolution, then sequentially add samarium metal powder, iodine, cuprous iodide powder;Instead
System is answered to be carried out under the conditions of anhydrous, under stirring until the reaction is complete;After obtained reaction mixture is post-treated, column color
Compose isolated 3,3- diphenyl -3- hydroxypropionitrile sterlings.
2. a kind of method of synthesis 3,3- diphenyl -3- hydroxypropionitriles according to claim 1, it is characterised in that used
Acetonitrile content be benzophenone dosage 1-3 times of mass ratio;Samarium powder dosage is the molar ratio 0.1-0.5 of benzophenone dosage
Times;The dosage of iodine is 0.01-0.05 times of the molar ratio of samarium powder dosage;Cuprous iodide dosage is the molar ratio 0.01- of samarium powder dosage
0.05 times.
3. a kind of method of synthesis 3,3- diphenyl -3- hydroxypropionitriles according to claim 1, it is characterised in that used
Reaction temperature be room temperature to 80 DEG C.
4. a kind of method of synthesis 3,3- diphenyl -3- hydroxypropionitriles according to claim 1, it is characterised in that reaction is not
Using other solvents.
5. a kind of method of synthesis 3,3- diphenyl -3- hydroxypropionitriles according to claim 1, it is characterised in that used
Coupling metal be samarium.
6. a kind of method of synthesis 3,3- diphenyl -3- hydroxypropionitriles according to claim 1, it is characterised in that reacted
Journey is one kettle way single step reaction, yield 90-99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810780716.6A CN108689880B (en) | 2018-07-16 | 2018-07-16 | Solvent-free method for preparing diphenyl hydroxyl propionitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810780716.6A CN108689880B (en) | 2018-07-16 | 2018-07-16 | Solvent-free method for preparing diphenyl hydroxyl propionitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108689880A true CN108689880A (en) | 2018-10-23 |
| CN108689880B CN108689880B (en) | 2020-12-22 |
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| CN201810780716.6A Active CN108689880B (en) | 2018-07-16 | 2018-07-16 | Solvent-free method for preparing diphenyl hydroxyl propionitrile |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014122811A1 (en) * | 2013-02-07 | 2014-08-14 | 国立大学法人名古屋大学 | Coupling method and method for producing aromatic group-substituted heterocyclic compound using said coupling method |
| CN106946901A (en) * | 2017-04-06 | 2017-07-14 | 青岛科技大学 | A kind of plain precursor of rosin and its synthetic method |
| CN106957323A (en) * | 2017-04-06 | 2017-07-18 | 青岛科技大学 | A kind of simple and easy method for synthesizing sesamin precursor |
-
2018
- 2018-07-16 CN CN201810780716.6A patent/CN108689880B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014122811A1 (en) * | 2013-02-07 | 2014-08-14 | 国立大学法人名古屋大学 | Coupling method and method for producing aromatic group-substituted heterocyclic compound using said coupling method |
| CN106946901A (en) * | 2017-04-06 | 2017-07-14 | 青岛科技大学 | A kind of plain precursor of rosin and its synthetic method |
| CN106957323A (en) * | 2017-04-06 | 2017-07-18 | 青岛科技大学 | A kind of simple and easy method for synthesizing sesamin precursor |
Non-Patent Citations (3)
| Title |
|---|
| EDWIN M. KAISER AND CHARLES R. HAUSER: "Ionization of an a Hydrogen of Acetonitrile by n-Butyllithium and Alkali Amides. Condensations with Ketones and Aldehydes to Form β-Hydroxynitriles", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| MURAHASHI, S.-I.: "Synthesis from nitriles with retention of the cyano group", 《SCIENCE OF SYNTHESIS》 * |
| YONGJUN LIU等: "A novel coupling reaction of α-halo ketones promoted by SmI3/CuI", 《RSC ADV.》 * |
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| Publication number | Publication date |
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| CN108689880B (en) | 2020-12-22 |
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