CN105820136A - Preparation method of first-class benzoxazine compound - Google Patents
Preparation method of first-class benzoxazine compound Download PDFInfo
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- CN105820136A CN105820136A CN201610335917.6A CN201610335917A CN105820136A CN 105820136 A CN105820136 A CN 105820136A CN 201610335917 A CN201610335917 A CN 201610335917A CN 105820136 A CN105820136 A CN 105820136A
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- benzoxazine compound
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- 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
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/36—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings condensed with one six-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention relates to a preparation method of a first-class benzoxazine compound .The structural formula of the prepared benzoxazine compound is shown in the drawing, wherein R1 is a hydrogen atom, an alkyl group, an aryl group, halogen, an alkoxy group, an aryloxy group, a trifluoromethyl group and the like .The preparation method includes the steps that ortho-aminophenol and dibenzoyl serve as the reaction raw materials, 1,2-dichloroethane serves as the solvent, under the catalysis of acid, a molecular sieve is added, reaction is conducted at the temperature of 60 DEG C for 10 hours, after reaction ends, extraction and condensation are conducted, column chromatography isolation is conducted to obtain a benzoxazine compound intermediate, under the catalysis of alkali, 1,2-dichloroethane serves as the solvent, reaction is conducted at the temperature of 80 DEG C for 8 hours, condensation is conducted, and column chromatography purification is conducted to obtain the product compound .The yield is 60-80%, and alkali is sodium hydride, calcium hydride, potassium hydride, tertiary butanol alkali and the like.
Description
Technical field
The present invention is the preparation method of a class benzoxazine compounds.
Background technology
Benzoxazine is phenolic resinoid substitute products, existing phenolic resin feature, overcome again its product
The shortcoming of release small-molecule substance etc. during fragility big solidification.Its good characteristic makes it at fire proofing, electronic package material, electricity
The fields such as insulant are widely used.As far back as nineteen forty-four holly and cope with o-hydroxy methylamine and formaldehyde it is
Raw material carries out having been surprisingly found that benzoxazine during the synthesis of Mannich product.Cause the concern of widely studied person afterwards.This
Bright propose a kind of method synthesizing benzoxazine compounds.The present invention is with o-aminophenol compounds as raw material, in acid
Reacting with benzil under the conditions of property, generate benzoxazine compounds intermediate, this benzoxazine compounds intermediate is at alkali
Lower rearrangement of catalysis generate a kind of new benzoxazine compounds.The present invention has simple to operate, and reaction condition is gentle, synthesis
Technique and purification process simple yield advantages of higher.
Summary of the invention
One purpose of the present invention is to provide a kind of method preparing above-claimed cpd.
For achieving the above object, benzoxazine compounds structure such as Fig. 1, wherein R that the present invention provides1For hydrogen atom,
Alkyl, aryl, halogen, alkoxyl, aryloxy group, trifluoromethyl etc..The preparation method that the present invention provides, has main steps that: adjacent ammonia
Base phenol and dibenzoyl are reaction raw materials, and 1,2-dichloroethanes makees solvent, add the 60 ° of C reactions 10 of catalyst p-methyl benzenesulfonic acid
Hour, after reaction terminates, extraction concentrates, and column chromatography for separation obtains a kind of benzoxazine intermediate (such as Fig. 2-A).This compound exists
Under the catalysis of alkali, 1,2-dichloroethanes makees solvent, after reacting 8 hours, concentrates under 80 ° of C temperature conditionss, and column chromatography purifies,
To product.Productivity is 60% ~ 80%.Wherein alkali is sodium hydride, calcium hydride, hydrofining, tert-butyl alcohol alkali etc..
Gained compound through nmr spectrum (1H-NMR and13C-NMR), structure is errorless.
The present invention uses substituted or unsubstituted o-aminophenol and the benzil can the most commercially.
The catalyst that the present invention uses is p-methyl benzenesulfonic acid (0.2 equivalent), potassium tert-butoxide (2 equivalents).
Eluant used by the column chromatography of the present invention is petroleum ether and ethyl acetate (volume ratio 5:1).
Accompanying drawing explanation
Fig. 1 is benzoxazine compounds structure chart；
Fig. 2 is detailed description of the invention procedure chart.
Detailed description of the invention
Its course of reaction is as shown in Figure 2.
Concrete preparation method: o-aminophenol and dibenzoyl (the amount ratio of 1:1 material) are put into reaction tube, 0.2 equivalent
P-methyl benzenesulfonic acid, is subsequently adding 1 mL 1,2-dichloroethanes, molecular sieve, and 60 ° of C react 10 hours；After reaction terminates, extract dense
Contracting, column chromatography purifies, and eluant is petroleum ether and ethyl acetate (volume ratio 5:1), obtains in the middle of a kind of benzoxazine compound
Body (such as Fig. 2-A), yield is 80%；Intermediate, under (2 equivalents) of sodium hydride is catalyzed, adds a little dichloroethanes, at 80 °
React 8 hours under C temperature conditions, after reaction terminates, extraction, concentrate, column chromatography purifies, and eluant is petroleum ether and ethyl acetate
(volume ratio 5:1), obtains product, and productivity is 70%；Proton nmr spectra: 1 H-NMR (400 MHz, DMSO-d 6) δ
10.08 (s, 1H) , 8.11-8.08 (m, 2H) , 7.84-7.82 (m,2H) , 7.71-7.65 (m, 2H) ,
7.56-7.51 (m, 3H), 7.46-7.40 (m, 3H), 7.36-7.34 (m, 2H), carbon-13 nmr spectra: 13 C-
NMR (100 MHz, DMSO-d 6 ) δ 165.3, 163.7, 144.4, 134.1, 133.7, 131.4, 130.1,
129.5, 129.0, 128.6, 128.2, 127.4, 126.6, 126.0, 125.8, 123.2。
The present invention relates to the preparation method of a class benzoxazine compounds.It is reaction by o-aminophenol and dibenzoyl
Material synthesis one benzoxazine compounds intermediate, resets the most in the basic conditions and obtains new type heterocycle benzoxazine class
Compound.The present invention has simple to operate, and reaction condition is gentle, synthesis technique and purification process simple yield advantages of higher.
Claims (2)
1. the method preparing compound claims, has main steps that:
A) o-aminophenol and dibenzoyl (1:1, the amount ratio of material) are put into reaction tube, the p-methyl benzenesulfonic acid of 0.2 equivalent,
Being subsequently adding a little 1,2-dichloroethanes, molecular sieve, 60 ° of C react 10 hours；
B) after reaction terminates, extraction concentrates, and column chromatography purifies, and eluant is petroleum ether and ethyl acetate (volume ratio 5:1),
To a kind of benzoxazine compound intermediate；
C), under (2 equivalents) at sodium hydride is catalyzed, adds 1 mL1,2-dichloroethanes, under 80 ° of C temperature conditionss, react 8 little
Time, after reaction terminates, extraction, concentrate, column chromatography purifies, and eluant is petroleum ether and ethyl acetate (5:1), obtains product.
2. the catalyst that the present invention uses is p-methyl benzenesulfonic acid (0.2 equivalent) and sodium hydride (2 equivalents), and solvent is two chloroethenes
Alkane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610335917.6A CN105820136A (en) | 2016-05-20 | 2016-05-20 | Preparation method of first-class benzoxazine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610335917.6A CN105820136A (en) | 2016-05-20 | 2016-05-20 | Preparation method of first-class benzoxazine compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105820136A true CN105820136A (en) | 2016-08-03 |
Family
ID=56530187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610335917.6A Withdrawn CN105820136A (en) | 2016-05-20 | 2016-05-20 | Preparation method of first-class benzoxazine compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105820136A (en) |
-
2016
- 2016-05-20 CN CN201610335917.6A patent/CN105820136A/en not_active Withdrawn
Non-Patent Citations (3)
| Title |
|---|
| ERICH TAUER ET AL.: "Photochemical and Thermal Reactions of Aromatic Schiff Bases", 《J. ORG. CHEM.》 * |
| KATAYOUN MARJANI ET AL.: "Oxidative cleavage of a cyclic hemiketal in the presence of copper(II) and structural characterization of the product complex", 《TRANSITION MET CHEM》 * |
| 陈永: "苯甲酰胺/苯并噁唑及苯并噁唑烷类化合物的合成研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20160803 |