CN106397130A - Preparation method for 5-hydroxyl-5-phenylacetylene dibenzosuberenone - Google Patents
Preparation method for 5-hydroxyl-5-phenylacetylene dibenzosuberenone Download PDFInfo
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- CN106397130A CN106397130A CN201610221238.6A CN201610221238A CN106397130A CN 106397130 A CN106397130 A CN 106397130A CN 201610221238 A CN201610221238 A CN 201610221238A CN 106397130 A CN106397130 A CN 106397130A
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- phenylacetylene
- dibenzosuberenone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method for 5-hydroxyl-5-phenylacetylene dibenzosuberenone. The preparation method comprises the following steps: adding tetrahydrofuran into a reaction vessel, carrying out stirring and cooling, then replacing air therein with nitrogen gas, adding lithium amide, and dropwise adding phenylacetylene; carrying out a reaction at room temperature for 0.3 to 0.8 hour, adding 5-dibenzosuberenone in one time, and carrying out heating reflux; after the reaction is completed, stopping the reaction, and carrying out cooling to room temperature; and carrying out separation by adding water and an organic solvent into the above-mentioned reaction vessel, then combining an organic phase, carrying out purifying through a silica gel column, and carrying out concentration and drying so as to obtain the 5-hydroxyl-5-phenylacetylene dibenzosuberenone. According to the invention, the 5-hydroxyl-5-phenylacetylene dibenzosuberenone is obtained through a reaction of 5-dibenzosuberenone and phenylacetylene under the action of a catalyst namely lithium amide. The preparation method provided by the invention has the advantages of no harsh reaction conditions, high yield and applicability to industrial production.
Description
Technical field
The invention belongs to chemical field, it is related to a kind of preparation method of 5- hydroxyl -5- phenylacetylene dibenzosuberenone.
Background technology
5- hydroxyl -5- phenylacetylene dibenzosuberenone is a kind of important intermediate, and this compound can be used for synthesizing a kind of new coating material
Material, this new coating material phosphorus content is high, have good corrosion stability, can be used for multilayer photoetching, adapts to that semi-conductor industry is less to be received
The Improvement requirement of meter Jie Dian.
The complex process of this compound is prepared, reaction condition will be carried out under conditions of -78 degrees Celsius, reaction condition will in prior art
Ask relatively harsh.Also the synthetic reaction having some similar structures is reported, but whether differential responses group can be smoothed out reacting, and
Not can determine that to the aspect such as product and purity.
Content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of system of 5- hydroxyl -5- phenylacetylene dibenzosuberenone
Preparation Method, the preparation method of described this 5- hydroxyl -5- phenylacetylene dibenzosuberenone will solve acquisition 5- hydroxyl in prior art
Base -5- phenylacetylene dibenzosuberenone needs at very low temperature just obtainable technical problem, and the present invention passes through to select suitable temperature
Degree and reagent, are successfully completed reaction and obtain product, and environmentally safe.
The invention provides a kind of preparation method of 5- hydroxyl -5- phenylacetylene dibenzosuberenone, comprise the steps：
1) in a reaction vessel, it is initially charged oxolane, stirs and be cooled to 0～10 DEG C, with nitrogen displacement wherein
Air, be subsequently adding lithium amide, then drip phenylacetylene；After room temperature reaction 0.3～0.8 hour, disposably add 5-
Dibenzosuberenone, is heated to reflux 2～4h, described 5- dibenzosuberenone, phenylacetylene, lithium amide and tetrahydrochysene furan
The material ratio muttered is 1mol：1～2mol：1～2mol：1500～3000mL；After reaction completely, stop reaction, be cooled to
Room temperature；
2) also include a step isolating and purifying, carried out by adding water and organic solvent in above-mentioned reaction vessel
Separate, be then combined with organic phase, after silicagel column purifies, concentrates, removing solvent, obtain 5- hydroxyl -5- phenylacetylene hexichol
And cycloheptyl ketenes.
Further, in a described step isolating and purifying, in first reaction vessel, add water, stand after stirring, point
Liquid, separates organic layer, then adds organic solvent in aqueous phase addition, stirring, and standing separates organic layer, then in water layer
Add organic solvent, stirring, standing, separate organic layer, merge organic phase, add silica gel, reduced pressure concentration, use petroleum ether
Carried out post, obtained product organic phase, after inspissated oil ether, then drawn with oil pump dry that product is yellow gummy solid 5- hydroxyl
Base -5- phenylacetylene dibenzosuberenone.
The reaction equation of the present invention is：
During the course of the reaction, plus during lithium amide, temperature rise very fast, so this reaction is carried out at 0～10 DEG C；Reaction terminates, in room
Temperature is lower to process unnecessary lithium amide；Because product is colloidal solid, certain solvent can be contained, so solvent must be removed.
The present invention compares with prior art, and its technological progress is significant.The present invention passes through 5- dibenzosuberenone, phenylacetylene is being urged
Carry out reaction in the presence of agent lithium amide and obtain 5- hydroxyl -5- phenylacetylene dibenzosuberenone.The reaction condition of the present invention is not harsh,
High income, is suitable for industrialized production.
Specific embodiment
Embodiment 1
1), material proportion：
2), operating procedure：
In the four round flask of 1000ml, add 500mlTHF, stir and be cooled to 5 DEG C, with nitrogen displacement, add lithium amide
(8.1g), drip phenylacetylene 37.2g, after (20～25 degree) reaction half an hour of room temperature, disposable addition 5- dibenzocycloheptene
Ketone (50g), is heated to reflux 3h, reaction (middle control 1) completely, stops reaction, is cooled to room temperature (20～25 degree).
Add water (250ml) in stirring downhill reaction liquid, stir 5 minutes, stand 10 minutes, point liquid, separate organic layer, aqueous phase adds
250ml ethyl acetate, stirs 10min, stands 10min, separates organic layer, and water layer adds ethyl acetate (250ml), stirs 10min,
Standing 10min, separates organic layer, merges organic phase, adds silica gel (75g), 60 degree of reduced pressure concentrations, with PE (petroleum ether) (4L)
Carried out post.Obtain product organic phase, after inspissated oil ether, then drawn with oil pump dry that product is yellow gummy solid 53g, yield is about
Record content 98% for 76%, HPLC.
Nuclear magnetic data：1H NMR(CDCl3,25℃),δ:3.12(s,1H,OH)；7.18 (s, 2H, CH=CH)；7.24-7.31(m,5
H,Ar-H.)；7.34-7.43(m,6H,Ar-H.)；8.10(d,2H,C≡C-Ar-H)
3), experimental result：
4) control in, reacting：
| Sample point | Sample treatment | Testing conditions | Detection method | Middle control standard |
| Middle control 1 | Clear liquid is taken to detect | TLC | PE:EA 10:1 | Raw material point disappears |
Claims (3)
1. a kind of preparation method of 5- hydroxyl -5- phenylacetylene dibenzosuberenone is it is characterised in that comprise the steps：
In a reaction vessel, it is initially charged oxolane, stirs and be cooled to 0 ~ 10 DEG C, with nitrogen displacement air therein, be subsequently adding lithium amide, then drip phenylacetylene；After room temperature reaction 0.3 ~ 0.8 hour, disposable addition 5- dibenzosuberenone, it is heated to reflux 2 ~ 4h, described 5- dibenzosuberenone, the material ratio of phenylacetylene, lithium amide and oxolane are 1mol：1~2 mol：1~2 mol：1500~3000mL；After reaction completely, stop reaction, be cooled to room temperature；
Also include a step isolating and purifying, carry out separating by adding water and organic solvent in above-mentioned reaction vessel, be then combined with organic phase, after silicagel column purifies, concentrates, removing solvent, obtain 5- hydroxyl -5- phenylacetylene dibenzosuberenone.
2. a kind of 5- hydroxyl -5- phenylacetylene dibenzosuberenone according to claim 1 preparation method it is characterised in that：In a described step isolating and purifying, add water in first reaction vessel, stand after stirring, point liquid, separate organic layer, then add organic solvent in aqueous phase addition, stirring, standing, separate organic layer, add organic solvent, stirring, standing in water layer again, separate organic layer, merge organic phase, add silica gel, reduced pressure concentration, carried out post with petroleum ether, obtain product organic phase, after inspissated oil ether, then drawn with oil pump dry that product is yellow gummy solid 5- hydroxyl -5- phenylacetylene dibenzosuberenone.
3. a kind of 5- hydroxyl -5- phenylacetylene dibenzosuberenone according to claim 1 preparation method it is characterised in that：Described 5- dibenzosuberenone, the material ratio of phenylacetylene, lithium amide and oxolane are 1mol：1 .5mol：1.5 mol：2000mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610221238.6A CN106397130A (en) | 2016-04-11 | 2016-04-11 | Preparation method for 5-hydroxyl-5-phenylacetylene dibenzosuberenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610221238.6A CN106397130A (en) | 2016-04-11 | 2016-04-11 | Preparation method for 5-hydroxyl-5-phenylacetylene dibenzosuberenone |
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| Publication Number | Publication Date |
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| CN106397130A true CN106397130A (en) | 2017-02-15 |
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| CN201610221238.6A Pending CN106397130A (en) | 2016-04-11 | 2016-04-11 | Preparation method for 5-hydroxyl-5-phenylacetylene dibenzosuberenone |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017041A (en) * | 2015-06-12 | 2015-11-04 | 北京科技大学 | Dibenzosuberan enone derivatives and preparation method therefor and application thereof |
-
2016
- 2016-04-11 CN CN201610221238.6A patent/CN106397130A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017041A (en) * | 2015-06-12 | 2015-11-04 | 北京科技大学 | Dibenzosuberan enone derivatives and preparation method therefor and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| SARAH A. BRUSEY等: "X-ray Crystallographic and NMR Spectroscopic Study of (η2-Alkene) (μ-alkyne) pentacarbonyldicobalt Complexes: Arrested Pauson-Khand Reaction Intermediates", 《ORGANOMETALLICS》 * |
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Effective date of registration: 20201116 Address after: 221300 chemical agglomeration area, Pizhou Economic Development Zone, Jiangsu, Xuzhou Applicant after: XUZHOU B&C CHEMICAL Co.,Ltd. Address before: 200092, room 4, building 333, 702 Guiping Road, Shanghai, Xuhui District Applicant before: SHANGHAI B&C CHEMICAL Co.,Ltd. Applicant before: XUZHOU B&C CHEMICAL Co.,Ltd. |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170215 |
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