CN103694298B - A kind of high optical activity amide compound and preparation method thereof - Google Patents
A kind of high optical activity amide compound and preparation method thereof Download PDFInfo
- Publication number
- CN103694298B CN103694298B CN201310713292.9A CN201310713292A CN103694298B CN 103694298 B CN103694298 B CN 103694298B CN 201310713292 A CN201310713292 A CN 201310713292A CN 103694298 B CN103694298 B CN 103694298B
- Authority
- CN
- China
- Prior art keywords
- cholesterol
- amide compound
- optical activity
- preparation
- high optical
- 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
Abstract
The present invention relates to a kind of high optical activity amide compound and preparation method thereof.The structural formula of described amide compound is:Its preparation method is cholesterol and solvent solution-forming, adds diisocyanate and catalyst under inert atmosphere and uniform temperature, and reactant obtains powder prepolymer after precipitating, filter, drying；Binaphthyl diphenol and solvent solution-forming, add prepolymer under uniform temperature after dissolving, product, again after precipitating, filter, wash, drying, i.e. obtains high optical activity amide compound.The features, the particularly preparation of diisocyanate cholesterol monoesters prepolymer such as the technical process that the present invention has preparation is easy, and process conditions are simple, and the controllability of experiment is strong, raw material is easy to get, and method is simple and easy to control.
Description
Technical field
The invention belongs to organic functional material prepares category, particularly relates to a kind of high optical activity amide compound and system thereof
Preparation Method.
Background technology
Optically active polymer is a kind of macromolecule with optically-active characteristic, point natural and synthetic two kinds.It is 50
The novel high polymer that mid-nineties 90 grows up.From structure, it has Configurational specificity and the band spiral of band chiral atom
Conformation specific both unsymmetrical factors of structure, these special structures give its rotary light performance, and polarized light can be made to send out
Raw deflection.Different high molecular optical activities and optical direction are different.Optically active polymer can do derivant, catalyst
Deng, it has the character of uniqueness in terms of photoelectric properties simultaneously, has more application at present in terms of military and civilian.Optical activity gathers
Containing polar amide groups and nonpolar carbochain in amide structure, it is readily obtained liquid crystalline phase structure.Its synthetic method has melted
Polycondensation, interfacial polycondensation, low temperature condensation etc..At present, to disclose a kind of optically-active polyurethane-urea infrared low for patent CN101696260A
Penetrate rate material, be mainly polymerized by hydrogen migration addition three monomer of binaphthyl diphenol and diisocyanate and obtain；Patent
CN103087105A discloses a kind of chiral phosphine ligand or its enantiomer, raceme or diastereomer and comprises this part
Transition-metal catalyst, main by catalytic asymmetric hydrogenation thus be efficiently synthesized the chiral beta-virtue of high-optical-purity
Base amide compound.
Summary of the invention
The invention aims to improve the deficiencies in the prior art and a kind of high optical activity amide compound is provided, this
Bright another object is to provide the preparation method of above-mentioned high optical activity amide compound；The present invention can get multiple different optically-active side
To the high optical activity amide compound with optical rotation, this compound has good crystallinity, heat stability and high optical activity.
The object of the invention technical scheme is: a kind of high optical activity amide compound, it is characterised in that structural formula is as follows:
Present invention also offers the preparation method of above-mentioned high optical activity amide compound, it specifically comprises the following steps that
(1) under inert atmosphere protection, reaction monomers cholesterol and organic solvent are stirred to monomer at 75～90 DEG C
After dissolving, add isocyanates and pyridine, continue stirring reaction 30～40 hours；The solution that reaction obtains after terminating, through decompression
Distill adding in petroleum ether after solvent removal, filter after ice-water bath is placed 20～30 hours, after vacuum drying, obtain pre-polymerization
Thing diisocyanate cholesterol monoesters, wherein cholesterol, organic solvent, the mass ratio of pyridine are 1:(40～50): (0.003～
0.01), cholesterol and isocyanates mol ratio are 1:(1～1.5), petroleum ether is (3～5) with the volume ratio of organic solvent: 1；
(2) adding the mol ratio with cholesterol in the organic solvent of 60～100 times of cholesterol quality is 1:(2～2.5)
Binaphthyl diphenol, stir after dissolving to binaphthyl diphenol under inert atmosphere protection under 70～90 DEG C of constant temperature, add in step (1)
The prepolymer arrived, obtains solution after continuing stirring reaction 10～20 hours；
(3) obtaining adding in reaction solution in step (2) with the ratio of organic solvent volume in step (1) is (5～10): 1
Ethanol, ice-water bath is placed sucking filtration after 20～30 hours, after washing with alcohol, by the powder that obtains through the vacuum of 40～80 DEG C
Obtain high optical activity amide compound after drying.
The noble gas used by inert atmosphere protection described in preferred steps (1) is nitrogen or argon.Preferred steps
(1) isocyanates described in is hexamethylene diisocyanate, Toluene-2,4-diisocyanate, 4-diisocyanate or '-diphenylmethane diisocyanate
In one.Organic solvent described in preferred steps (1) is in N,N-dimethylformamide or DMAC N,N' dimethyl acetamide
A kind of；The N,N-dimethylformamide of more preferably GR level or DMAC N,N' dimethyl acetamide.
Binaphthyl diphenol described in preferred steps (2) is R-binaphthyl diphenol or S-binaphthyl diphenol.Pre-polymerization in preferred steps (2)
Thing is (2-2.5) with the mol ratio of binaphthyl diphenol: 1.Washing with alcohol 3～5 times in preferred steps (3).
The high general melt temperature of optical activity amide compound prepared by the present invention is 90～120 DEG C, and heat decomposition temperature is more than
250～270 DEG C, optical rotation absolute value is 200～300 °.
The present invention is a kind of high optical activity amide compound and preparation method thereof, and design synthesizes under catalyst action by gallbladder
Sterin and diisocyanate prepare prepolymer, and binaphthyl diphenol structure are introduced in compound by hydrogen transfer reaction, thus
To the amide compound with stable high optical rotation.
Beneficial effect:
(1) using two step synthesis, the technical process of preparation is easy, and process conditions are simple, and the controllability of experiment is strong.
(2) by the effect of catalyst, the cholesterol being made up of steroid moiety and side chain is introduced in prepolymer, for chemical combination
The high optical activity of thing provides basis.
(3) utilizing high activity functional group-NCO in prepolymer, the binaphthyl diphenol the 3rd that itself has certain optical activity is single
Body introduces in compound.By regulating the optical purity of Third monomer, can be formed and there is good crystallinity, heat stability and optics
The amide compound that activity is high.
Accompanying drawing explanation
Fig. 1 is the FT-IR figure of the high optical activity amide compound that example 1 prepares.
Fig. 2 is the hot polarisation photo of the high optical activity amide compound that example 1 prepares.
Fig. 3 is the TG figure of the high optical activity amide compound that example 1 prepares.
Detailed description of the invention
Example 1
It is 1:40 wiring solution-forming in mass ratio by reaction monomers cholesterol and GR level N,N-dimethylacetamide, under N2 protection
Under 80 DEG C of constant temperature after stirring and dissolving, dropping and mol ratio is 1.1:1 the 1 of cholesterol, hexamethylene-diisocyanate and solid with gallbladder
The mass ratio of alcohol is the pyridine of 1:200, obtains solution after reaction 40h.Solution, after decompression distillation desolvation, adds and N, N-
Dimethyl acetylamide volume ratio is in the petroleum ether of 5:1, filters, the product obtained after filtration, vacuum in ice-water bath after placing 30h
It is dried to obtain white powder prepolymer hexamethylene diisocyanate cholesterol monoesters；It is 1:2.1 by the mol ratio with cholesterol
S-binaphthyl diphenol and the N,N-dimethylacetamide wiring solution-forming of 60 times of S-binaphthyl diphenol quality, N2 protection under at 90 DEG C of constant temperature
Adding after lower stirring and dissolving with S-binaphthyl diphenol mol ratio is the prepolymer of 2.1:1, obtains solution and join and N after reaction 15h,
N-dimethyl acetylamide volume ratio is in the ethanol of 10:1, places sucking filtration after 30h in ice-water bath, after washing with alcohol 3 times, by powder
It is placed in 50 DEG C of vacuum drying ovens and is dried to obtain high optical activity amide compound.The optical rotation of high optical activity amide compound is
250°。
The FT-IR of the high optical activity amide compound obtained by this example schemes as shown in Figure 1.From fig. 1, it can be seen that 3487 Hes
3404cm-1Place's two sharp-pointed characteristic absorption peaks of Binaphthol and 2100cm-1The characteristic absorption peak of-NCO all disappear；Due to
Naphthalene plane produces the reasons such as conjugation with ammonia ester bond, and product is at 1650cm-1Near occur in that by prepolymer diisocyanate gallbladder
In-the OCONH-that-NCO in sterin monoesters and the-OH reaction in binaphthyl diphenol generate, the absorption of vibrations of carbonyl, thus illustrates to close
Becoming product is required high optically-active amide compound.
The hot polarisation photo of the high optical activity amide compound obtained by this example is as shown in Figure 2.From Fig. 2 and data record
Understanding, the melt temperature of high optical activity amide compound is 120 DEG C, and it shows high crystallization speed during heating and cooling
Rate, and form certain ordered phase.
The TG of the high optical activity amide compound obtained by this example schemes as shown in Figure 3.As can be seen from Figure 3, high optical activity acyl
The heat decomposition temperature of amines is 258 DEG C, possesses good heat stability.
Example 2
It is 1:50 wiring solution-forming in mass ratio by reaction monomers cholesterol and GR level DMF, N2Under protection
Under 85 DEG C of constant temperature after stirring and dissolving, dropping and the Toluene-2,4-diisocyanate that mol ratio is 1.2:1 of cholesterol, 4-diisocyanate and and gallbladder
The mass ratio of sterin is the pyridine of 1:100, obtains solution after reaction 32h.Solution, after decompression distillation desolvation, adds and N,
Dinethylformamide volume ratio is in the petroleum ether of 4:1, filters, the product obtained after filtration, very in ice-water bath after placing 24h
Sky is dried to obtain white powder prepolymer Toluene-2,4-diisocyanate, 4-diisocyanate cholesterol monoesters；By the mol ratio with cholesterol it is
The R-binaphthyl diphenol of 1:2.2 and the DMF wiring solution-forming of 80 times of R-binaphthyl diphenol quality, N290 under protection
Adding after stirring and dissolving with R-binaphthyl diphenol mol ratio under DEG C constant temperature is the prepolymer of 2.2:1, obtains solution and add after reaction 18h
To with the ethanol that DMF volume ratio is 8:1, ice-water bath places sucking filtration after 24h, after washing with alcohol 4 times,
Powder is placed in 60 DEG C of vacuum drying ovens and is dried to obtain high optical activity amide compound.The optical rotation of high optically-active amide compound is
260 °, infrared spectrum, hot polarisation photo are similar to example 1 to TG figure.
Example 3
It is 1:50 wiring solution-forming in mass ratio by reaction monomers cholesterol and GR level DMF, argon shield
Under under 90 DEG C of constant temperature after stirring and dissolving, the '-diphenylmethane diisocyanate that mol ratio is 1.5:1 of dropping and cholesterol and with
The mass ratio of cholesterol is the pyridine of 1:300, obtains solution after reaction 36h.Solution through decompression distillation desolvation after, add with
DMF volume ratio is in the petroleum ether of 3:1, filters, the product obtained after filtration in ice-water bath after placing 20h,
Vacuum drying obtains white powder prepolymer '-diphenylmethane diisocyanate cholesterol monoesters；By the mol ratio with cholesterol it is
The S-binaphthyl diphenol of 1:2.5 and the DMF wiring solution-forming of 90 times of S-binaphthyl diphenol quality, under argon shield
Under 70 DEG C of constant temperature after stirring and dissolving, adding with S-binaphthyl diphenol mol ratio is the prepolymer of 2.5:1, obtains solution after reaction 20h
Join with the ethanol that DMF volume ratio is 6:1, ice-water bath is placed sucking filtration after 20h, washing with alcohol 5 times
After, powder is placed in 80 DEG C of vacuum drying ovens and is dried to obtain high optical activity amide compound.The optically-active of high optically-active amide compound
Degree is 230 °, and infrared spectrum, hot polarisation photo are similar to example 1 to TG figure.
Claims (4)
1. the method preparing high optical activity amide compound, it specifically comprises the following steps that
(1) under inert atmosphere protection, reaction monomers cholesterol and organic solvent are stirred at 75～90 DEG C to monomer dissolving
After, add isocyanates and pyridine, continue stirring reaction 30～40 hours；The solution that reaction obtains after terminating, through decompression distillation
By adding in petroleum ether after solvent removal, filter after ice-water bath is placed 20～30 hours, after vacuum drying, obtain prepolymer two
Isocyanates cholesterol monoesters, wherein cholesterol, organic solvent, the mass ratio of pyridine are 1:(40～50): (0.003～
0.01), cholesterol and isocyanates mol ratio are 1:(1～1.5), petroleum ether is (3～5) with the volume ratio of organic solvent: 1；
Wherein said isocyanates is hexamethylene diisocyanate；
(2) adding in the organic solvent of 60～100 times of cholesterol quality with the mol ratio of cholesterol is 1:(2～2.5) connection
Naphthalenediol, stirs after dissolving to Binaphthol under 70～90 DEG C of constant temperature, obtains in addition step (1) under inert atmosphere protection
Prepolymer, obtains solution after continuing stirring reaction 10～20 hours；Wherein said Binaphthol is R-Binaphthol or S-connection
Naphthalenediol；
(3) obtaining adding in reaction solution in step (2) with the ratio of organic solvent volume in step (1) is (5～10): the second of 1
Alcohol, places sucking filtration after 20～30 hours in ice-water bath, after washing with alcohol, by the powder that obtains through the vacuum drying of 40～80 DEG C
After obtain high optical activity amide compound；The structural formula of obtained high optical activity amide compound is as follows:
Optical rotation absolute value is 200～300 °.
Preparation method the most according to claim 1, it is characterised in that in step (1), inert atmosphere is nitrogen or argon.
Preparation method the most according to claim 1, it is characterised in that the organic solvent described in step (1) is N, N-bis-
One in methylformamide or DMAC N,N' dimethyl acetamide.
Preparation method the most according to claim 1, it is characterised in that prepolymer and the mol ratio of Binaphthol in step (2)
For (2-2.5): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310713292.9A CN103694298B (en) | 2013-12-23 | 2013-12-23 | A kind of high optical activity amide compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310713292.9A CN103694298B (en) | 2013-12-23 | 2013-12-23 | A kind of high optical activity amide compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103694298A CN103694298A (en) | 2014-04-02 |
| CN103694298B true CN103694298B (en) | 2016-08-31 |
Family
ID=50355983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310713292.9A Active CN103694298B (en) | 2013-12-23 | 2013-12-23 | A kind of high optical activity amide compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103694298B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199747B (en) * | 2015-10-20 | 2017-12-15 | 京东方科技集团股份有限公司 | A kind of composition, liquid crystal display panel and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696260A (en) * | 2009-10-12 | 2010-04-21 | 东南大学 | Polarimetric polyurethane-urea infrared low emissivity material and preparation method thereof |
| CN101870761A (en) * | 2010-06-13 | 2010-10-27 | 东南大学 | Optical rotation polyurethane-imide infrared low-emissivity material and preparation method thereof |
| CN102643432A (en) * | 2012-04-01 | 2012-08-22 | 北京科技大学 | Preparation method for cholesteric siloxane side-chain liquid crystal polymer |
| US8455061B2 (en) * | 2010-04-02 | 2013-06-04 | Jnc Corporation | Optically active compound having polymerizable group and its polymer |
-
2013
- 2013-12-23 CN CN201310713292.9A patent/CN103694298B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696260A (en) * | 2009-10-12 | 2010-04-21 | 东南大学 | Polarimetric polyurethane-urea infrared low emissivity material and preparation method thereof |
| US8455061B2 (en) * | 2010-04-02 | 2013-06-04 | Jnc Corporation | Optically active compound having polymerizable group and its polymer |
| CN101870761A (en) * | 2010-06-13 | 2010-10-27 | 东南大学 | Optical rotation polyurethane-imide infrared low-emissivity material and preparation method thereof |
| CN102643432A (en) * | 2012-04-01 | 2012-08-22 | 北京科技大学 | Preparation method for cholesteric siloxane side-chain liquid crystal polymer |
Non-Patent Citations (6)
| Title |
|---|
| Chiral nematic liquid crystals with helix inversion from (R)-1,1′-binaphthyl and cholesteryl ester moieties;Cheng ZH, et al.;《Liquid Crystals》;20120810;第39卷(第10期);第1284-1290页 * |
| Cholesterol-based nonsymmetric liquid crystal dimers: an overview;Yelamaggad CV, et al.;《Journal of Materials Chemistry》;20080527;第18卷;第2927-2949页 * |
| Helical polyurethane-imide@attapulgite composite：preparation, characterization and infrared emissivity study;Wang ZQ, et al.;《materials》;20100125;第64卷(第8期);第908-911页 * |
| 具有光学活性高性能高分子材料的研究进展;韩涛, 等.;《高分子材料科学与工程》;20111231;第27卷(第12期);第159-162,166页 * |
| 含联萘基团的新型旋光性聚（氨酯-酰亚胺）的制备与表征;南秋利, 等.;《化工新型材料》;20070630;第35卷(第6期);第23-26页 * |
| 热致型液晶聚氨酯弹性体的合成及性能表征;赵京欣;《中国优秀硕士学位论文全文数据库（工程科技I辑）》;20130615(第06期);正文第11-13页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103694298A (en) | 2014-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107473748B (en) | Preparation method of beryllium-containing silicon carbide ceramic fiber | |
| CN102643432A (en) | Preparation method for cholesteric siloxane side-chain liquid crystal polymer | |
| CN103992353A (en) | Flame retardant hexabutanol cyclotriphosphazene, and preparation method and application thereof | |
| CN105061711A (en) | DOPO type reactive flame retardant with terminal group as epoxy group, preparation method therefor and application thereof | |
| CN103289125B (en) | Phosphorus-nitrogen-silicon containing organic and inorganic hybrid fire retardant and preparation method thereof and formed polymer | |
| CN104558683A (en) | DOPO-containing cyclic phosphate flame retardant as well as preparation method and application thereof | |
| CN103044708A (en) | High-efficiency N/P flame retardant, as well as preparation method and application thereof | |
| CN101696260B (en) | Polarimetric polyurethane-urea infrared low emissivity material and preparation method thereof | |
| CN108441244A (en) | A kind of preparation method of mesocarbon microspheres and mesophase pitch | |
| CN101891896B (en) | Expansible fire retardant containing fluorine-phosphorus-nitrogen oligomer and preparation method thereof | |
| CN103664699B (en) | Autocatalytic nitrile resin monomer, polymer and preparation method of polymer | |
| CN111363148B (en) | Preparation method of binaphthyl network type polyimide resin and film and application of binaphthyl network type polyimide resin and film in gas separation | |
| CN103694298B (en) | A kind of high optical activity amide compound and preparation method thereof | |
| CN101245024A (en) | Process for producing 1,3-bis(2,4-diaminophenyloxy)benzene | |
| Yeşilot et al. | Stereochemical aspects of polyphosphazenes | |
| CN103224531A (en) | Synthetic method for P- and N-containing fire retardant | |
| KR20170045889A (en) | Method for preparing polyamide and polyamide prepared by using the same | |
| CN101613605A (en) | Spiro-phosphorus phenone polyesteramide intumescent fire retardant and synthetic method thereof | |
| CN1332963C (en) | Amino phenyl cage type sesqui siloxane and its preparing method | |
| CN101870693B (en) | Bismaleimide containing 1,3,4-oxadiazole structure and preparation method thereof | |
| CN102391226A (en) | Diamine monomer with phthalein structure and phenolic hydroxyl and preparation method thereof | |
| CN108017788B (en) | Double-tower type polyhedral oligomeric silsesquioxane containing metallic tin and preparation and application thereof | |
| CN103819308B (en) | A kind of curable poly-isophthalic and its preparation method and application | |
| CN114605602B (en) | Hierarchical pore covalent organic framework compound and preparation method and application thereof | |
| CN105503775A (en) | Diamine monomer with triphenylamine structure containing p-substituted cyclic amine, preparation method and application of diamine monomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |