CN106946738B - A method of synthesizing alpha-aminonitriles using AIBN as independent cyano sources - Google Patents
A method of synthesizing alpha-aminonitriles using AIBN as independent cyano sources Download PDFInfo
- Publication number
- CN106946738B CN106946738B CN201710176712.2A CN201710176712A CN106946738B CN 106946738 B CN106946738 B CN 106946738B CN 201710176712 A CN201710176712 A CN 201710176712A CN 106946738 B CN106946738 B CN 106946738B
- Authority
- CN
- China
- Prior art keywords
- aibn
- aminonitriles
- alpha
- independent
- independent cyano
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/08—Formation or introduction of functional groups containing nitrogen of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no 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
- C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no 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
- C07D211/60—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
Abstract
The method that the present invention relates to a kind of to synthesize alpha-aminonitriles using AIBN as independent cyano sources.Tertiary amine is added in container, 2,2'- azodiisobutyronitrile (AIBN), pivalic acid, sodium acetate and molecular sieve are then sequentially added, using methanol as solvent, reacts 7-9 hours, be cooled to room temperature at 85-95 DEG C, silica gel column chromatography separation, obtains target product.The present invention 2,2'- azodiisobutyronitrile (AIBN) is the nontoxic compound containing cyano, is typically used as radical initiator.The present invention using AIBN as the exclusive source in nitrile source, synthesizes a series of alpha-aminonitriles compound for the first time, and method is simple, non-toxic, and yield is high.
Description
Technical field
The invention belongs to the field of chemical synthesis, it is specifically related to that a kind of method is simple, using AIBN as the synthesis one in nitrile source
The method of the alpha-aminonitriles compound of series.
Background technique
Alpha-aminonitriles are not only to construct the precursor of nitrogenous bioactive compound (such as a-amino acid and steroids), and
It has been widely used in the numerous areas of synthesis.This dual-function compound is by generating imonium ion (electrophilic reagent) and carboxylic acid
Root (nucleopilic reagent) shows double reaction, is used to synthesize various valuable functional groups, including alpha-amido aldehyde, ketone and α-
Amino alcohol.Therefore, it develops very necessary for synthesizing the efficient and convenient method of alpha-aminonitriles.
The method of directly synthesis alpha-aminonitriles has had much at present, but the use in nitrile source can not get rid of always hypertoxicity
The problem of.Widely used cyano sources include organic cyanogen source of the inorganic salts such as KCN, NaCN and hypotoxicity, such as cyanalcohol, third
Dintrile, cyanoformic ester, phenylacetonitrile, trimethylsilyl nitrile etc..
Summary of the invention
In order to solve problem above, it is simple that the present invention provides a kind of method, and nitrile source is non-toxic, the high synthesis alpha-amido of yield
The method of nitrile compound.
The technical solution adopted by the present invention is that: a method of synthesizing alpha-aminonitriles, packet using AIBN as independent cyano sources
It includes following steps: tertiary amine is added in container, then sequentially add 2,2'- azodiisobutyronitrile (AIBN), pivalic acid, vinegar
Sour sodium and molecular sieve are reacted 7-9 hours at 85-95 DEG C, are cooled to room temperature using methanol as solvent, silica gel column chromatography separation,
Obtain target product；The structural formula of the tertiary amine such as (I) is shown,
Wherein, R is halogen or methoxyl group or nitro or C1-C10 alkane substituent group,
X is protium or oxygen element or methylene.
A kind of above-mentioned method that alpha-aminonitriles are synthesized using AIBN as independent cyano sources, the structure of the alpha-aminonitriles
Formula such as (II),
Wherein, R is halogen or methoxyl group or nitro or C1-C10 alkane substituent group,
X is protium or oxygen element or methylene.
A kind of above-mentioned method that alpha-aminonitriles are synthesized using AIBN as independent cyano sources, in molar ratio, tertiary amine:
AIBN: pivalic acid: sodium acetate=1:3:1.5:1.
A kind of above-mentioned method that alpha-aminonitriles are synthesized using AIBN as independent cyano sources, in silica gel column chromatography separation, punching
Lotion is the mixed liquor of petroleum ether and ethyl acetate.
A kind of above-mentioned method that alpha-aminonitriles are synthesized using AIBN as independent cyano sources, by volume, petroleum ether: acetic acid
Ethyl ester=5:1.
The beneficial effects of the present invention are: 2,2'- azodiisobutyronitriles (AIBN) are the nontoxic compounds containing cyano, lead to
It is commonly used for radical initiator.The present invention using AIBN as the exclusive source in nitrile source, synthesizes a series of alpha-amido nitrilation for the first time
Object is closed, method is simple, and non-toxic, yield is high.
Specific embodiment
Embodiment 1-16
Synthetic method: the tertiary amine 2 of 1.0mol is added in tube sealing, is then added AIBN, 1.5mol's of 3.0mol
Pivalic acid, the sodium acetate of 1.0mol, molecular sieve and methanol are as solvent.Reaction is heated to 90 DEG C of 8 hours of reaction, later
It is cooled to room temperature, is separated using silica gel column chromatography.Irrigation is petrol ether/ethyl acetate (5:1v/v).As a result such as table 1.Reaction
Formula is as follows:
Table 1
Claims (4)
1. a kind of method for synthesizing alpha-aminonitriles using AIBN as independent cyano sources, which comprises the steps of: by three
Grade amine is added in container, then sequentially adds 2,2'- azodiisobutyronitrile (AIBN), pivalic acid, sodium acetate and molecular sieve, with
Methanol is reacted 7-9 hours at 85-95 DEG C, is cooled to room temperature as solvent, and silica gel column chromatography separation obtains target product；It is described
Tertiary amine structural formula it is as follows,
The structural formula of the alpha-aminonitriles is as follows,
2. a kind of method for synthesizing alpha-aminonitriles using AIBN as independent cyano sources according to claim 1, feature exist
In, in molar ratio, tertiary amine: 2,2'- azodiisobutyronitriles: pivalic acid: sodium acetate=1:3:1.5:1.
3. a kind of method for synthesizing alpha-aminonitriles using AIBN as independent cyano sources according to claim 1, feature exist
In in silica gel column chromatography separation, irrigation is the mixed liquor of petroleum ether and ethyl acetate.
4. a kind of method for synthesizing alpha-aminonitriles using AIBN as independent cyano sources according to claim 3, feature exist
In, by volume, petroleum ether: ethyl acetate=5:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710176712.2A CN106946738B (en) | 2017-03-23 | 2017-03-23 | A method of synthesizing alpha-aminonitriles using AIBN as independent cyano sources |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710176712.2A CN106946738B (en) | 2017-03-23 | 2017-03-23 | A method of synthesizing alpha-aminonitriles using AIBN as independent cyano sources |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106946738A CN106946738A (en) | 2017-07-14 |
| CN106946738B true CN106946738B (en) | 2019-03-12 |
Family
ID=59473324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710176712.2A Active CN106946738B (en) | 2017-03-23 | 2017-03-23 | A method of synthesizing alpha-aminonitriles using AIBN as independent cyano sources |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106946738B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081821A (en) * | 2006-05-29 | 2007-12-05 | 成都圣洁环保有限责任公司 | Preparation of aromatic nitrile compound by waste-free circulation method |
| US8722893B2 (en) * | 2008-11-13 | 2014-05-13 | Basf Se | Process for manufacturing 5-chloromethyl-2,3-pyridine dicarboxylic acid anhydrides |
-
2017
- 2017-03-23 CN CN201710176712.2A patent/CN106946738B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 可见光光氧化还原催化的三级胺α 位C-H 氰基化反应;周泉泉 等;《化学学报》;20161007;第75卷;110—114 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106946738A (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104910104B (en) | A kind of method of utilization copper catalysis synthesizing dihydro furan derivatives | |
| CN110156645B (en) | Preparation method of florfenicol intermediate | |
| CN106946738B (en) | A method of synthesizing alpha-aminonitriles using AIBN as independent cyano sources | |
| CN105481721B (en) | A kind of preparation method of 2,3 dicyano ethyl propanoate | |
| WO2020134137A1 (en) | Method for synthesizing r-3-chloroalanine methyl ester hydrochloride | |
| CN109206419B (en) | Sakubi koji intermediate and preparation method and application thereof | |
| JP6028606B2 (en) | Method for producing amine compound | |
| CN103664826B (en) | A kind of preparation method of aminonaphthol compound | |
| Seo et al. | A New Method for the Preparation of β-Hydroxy Nitriles: Transformation of 3-Bromo-2-isoxazolines to β-Hydroxy Nitriles by Treatment of Alkanethiolates | |
| CN106748881B (en) | A kind of catalysis oxidation synthetic method of nitrile compounds | |
| CN109438414B (en) | Method for preparing benzo 1, 3-oxathiane-4-ketone | |
| CN108976179B (en) | Preparation method for preparing deuterated compound by using deuterium source as deuterium source | |
| CN109516958B (en) | Preparation method of 2, 4-dichloropyrimidine and derivatives thereof | |
| CN112094237A (en) | Synthesis method of fluorobenzene imidazole | |
| CN108129350B (en) | Preparation method of 2, 4-dichlorobenzonitrile | |
| CN104529903B (en) | The diphenyl-imidazole of 2 methyl 4,5 and 2, the synthetic method of 4,5 triphenyl-oxazoles | |
| CN108299269A (en) | A kind of synthetic method of MC-1568 | |
| CN107698533A (en) | A kind of method for preparing Linezolid | |
| CN113636952B (en) | Method for preparing 4-bromobenzamide | |
| CN103787903B (en) | Method for preparing levetiracetam intermediate 2-aminobutyric acid | |
| CN115677585B (en) | Synthesis process of formaldehyde pyrazole derivative | |
| CN110272360B (en) | Preparation method of florfenicol reducing substance intermediate | |
| CN109553553B (en) | Method for preparing isopropyl phenylimino ester | |
| CN110437212B (en) | Synthesis method of N-2-alkyl substituted 1,2,3-triazole | |
| CN109824562A (en) | A kind of environment-friendly preparation method of Z-3- selenium cyanic acid ester group propenone compound |
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 |