CN1263121A - Synthesis of chiral ring prepolymer - Google Patents
Synthesis of chiral ring prepolymer Download PDFInfo
- Publication number
- CN1263121A CN1263121A CN 00102090 CN00102090A CN1263121A CN 1263121 A CN1263121 A CN 1263121A CN 00102090 CN00102090 CN 00102090 CN 00102090 A CN00102090 A CN 00102090A CN 1263121 A CN1263121 A CN 1263121A
- Authority
- CN
- China
- Prior art keywords
- chiral
- acetone
- prepolymer
- hooc
- cooh
- 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.)
- Granted
Links
Abstract
The present invention belongs to synthesis technology of chiral cyclic prepolymer. It is characterized by utilizing introduction of 4,4'-difluorobenzophennone or 4,4'-dicarboxylbenzophenone to substitute hydrogen on hydroxide radical in BN to obtain easy-to-introduce chiral motif and converting a pair of antimer into two diastereomers, then synthesizing rigid chiral cyclic prepolymer with complete aromatic structure.
Description
The invention belongs to a kind of synthetic technology of chiral ring prepolymer.
At the occurring in nature of both macro and micro level, spirane structure is a general phenomenon, and spirane structure also is one of essential characteristic of life.At molecular level, having double-stranded nucleic acid is to be the known important spirane structure of people with the protein with α-Luo Xuanjiegou.The isotactic of synthetic and syndiotactic polypropylene also have spirane structure.Synthetic molecule with spirane structure for the exploratory development of origin of life, has crucial meaning.
Synthetic with characterize molecule and, caused countries in the world scientists' interest in recent years the research of its state of aggregation with spirane structure.People such as Mark Mascal design to have synthesized by the hydrogen bond self-assembly and form the double-stranded tryptophane azepine ring molecule of deriving.People such as Kyoko Nozaki design to have synthesized by what covalent linkage was formed has a double-stranded cyclic polyester.But their outstanding work only limits to design synthetic molecule with spirane structure.Recently, people such as Cheng Zhengdi have reported the synthetic double-stranded crystal that has, and this has also represented the molecule of the synthetic spirane structure of design, and study a new direction of its state of aggregation.
2,2 '-dihydroxyl-1,1 '-naphthyl naphthalene (hereinafter to be referred as BN) are chirality primitives commonly used, and BN is owing to the negative electricity repulsion between two hydroxyl oxygen atom, and making between two naphthalene nucleus has angle, causes asymmetric.Because the negative electricity repulsion of Sauerstoffatom is big, so its chiral structure is stable.Often be applied to synthetic small molecules, ring molecule, linear polymer with spirane structure.But two hydroxyls are as active function groups, close proximity, because space multistory hinders, behind a hydroxyl reaction, another hydroxyl is difficult to react again, gives that design is synthetic to bring very big difficulty.
In order to solve the introducing problem of chiral radicals.We adopt recently and introduce new active function groups replacement hydroxyl, make it both keep the stable of chirality primitive, can introduce smoothly in the designed target molecule again.
We adopt 4, and 4 '-difluoro benzophenone or 4,4 '-benzophenonedicarboxylic acid replace the hydrogen on the hydroxyl among the BN.The active function groups of resulting BN derivative is fluorine (F-BN-F) or carboxyl (HOOC-BN-COOH), because two its reactive behavioies of active function groups apart from each other are better than last two hydroxyls that repel mutually of BN greatly.Though hydroxyl changes ether into, but still kept repulsion between two Sauerstoffatoms, so the chirality primitive is still stable.
And we have found a brand-new phenomenon.BN can not carry out post by common silicagel column and separate the BN that obtains opticity.F-BN-F then can carry out post by common silicagel column with HOOC-BN-COOH to be separated, and obtains (-) F-BN-F of opticity, (-) HOOC-BN-COOH of (+) F-BN-F and opticity, (+) HOOC-BN-COOH.This discovery can be simplified the split process of BN, reduces the cost of opticity BN.By opticity F-BN-F, HOOC-BN-COOH, we design and have synthesized brand-new chiral ring prepolymer.
The monomer synthetic method is; BN and 4,4 '-difluoro benzophenone or 4,4 '-benzophenonedicarboxylic acid is 1 with mol ratio: 5-40 wherein 1: 10-20 is better; salt of wormwood is salt forming agent; be mixed to join in the organic polar solvent N for example, dinethylformamide (DMF) or N; N-N,N-DIMETHYLACETAMIDE (DMAC); nitrogen protection, organic solvent toluene 30-60ml band water backflow 4-40 hour got final product in general 8-12 hour.Underpressure distillation removes and desolvates, and through ethanol extrct dereaction thing, obtains chiral monomer.Productive rate is more than 95%.By common silica gel chromatographic column, be that moving phase is separated with hexanaphthene and acetone respectively.Obtain the chiral monomer F-BN-F of opticity, HOOC-BN-COOH.F-BN-F or HOOC-BN-COOH and bisphenols monomer such as Resorcinol; '-biphenyl diphenol; dihydroxyphenyl propane, bisphenol S, tetramethyl biphenyl diphenol etc.; with mol ratio 1: 1; salt of wormwood is salt forming agent, is mixed to join organic polar solvent DMF or DMAC and reacts nitrogen protection; reflux, the backflow of organic solvent toluene 30-60ml band water got final product in 4-40 hour general 8-12 hour.Underpressure distillation removes and desolvates, and through acetone extrct dereaction thing, obtains chiral ring prepolymer.Productive rate is about 90%.
Embodiment one
With 28.63 gram (0.1mol) BN and 436 gram (2mol) 4,4 '-difluoro benzophenone is mixed to join in the three-necked bottle that 1000mlDMF is housed, nitrogen protection, and stirring heating refluxes, and refluxes 6 hours with 40ml toluene band water.Underpressure distillation removes and desolvates, and obtains white crude product, obtains pure F-BN-F through separating to purify, and product is a yellow powder.Productive rate is 95%.
Embodiment two
Method such as embodiment one, with 4,4 '-difluoro benzophenone charging capacity changes 218 grams (1mol) into.Separating purifies obtains pure F-BN-F, and product is a yellow powder.Productive rate is 96%.
Embodiment three
Method such as embodiment one are changed to DMAC with DMF, also can obtain F-BN-F.Productive rate is 98%.
Embodiment four
Method such as embodiment one will extend to 12 hours the reaction times, also can obtain F-BN-F.Productive rate is 97%.
Embodiment five
Method such as embodiment one, with 4,4 '-difluoro benzophenone is changed to 135 gram (0.5mol) 4, and 4 '-benzophenonedicarboxylic acid can obtain HOOC-BN-COOH.Productive rate is 96%.
Embodiment six
Method such as embodiment five are changed to DMAC with DMF, also can obtain HOOC-BN-COOH.Productive rate is 95.5%.
Embodiment seven
Method such as embodiment five will extend to 8 hours the reaction times, also can obtain HOOC-BN-COOH.Productive rate is 95%.
Embodiment eight
In 0.05 meter of diameter, fill common silica gel in long 0.5 meter the glass open tubular column as stationary phase.1g F-BN-F is dissolved in the acetone of 2ml, moving phase adopts hexanaphthene to separate with acetone (acetone content is 10%).It is dextral F-BN-F that collection obtains optically-active.Change moving phase into hexanaphthene and acetone (acetone content is 90%) and stay F-BN-F wash-out in post.Obtaining optically-active is left-handed F-BN-F.
Embodiment nine
Implementation method such as embodiment eight are dissolved in 1 gram HOOC-BN-COOH in the acetone of 2ml, obtain the HOOC-BN-COOH of opticity.
Embodiment ten
With 3.41 gram (0.005mol) F-BN-F, the Resorcinol of 0.55 gram (0.005mol) is dissolved among the 100mlDMF, slowly is added drop-wise in the three-necked bottle that 400mlDMF and 2 gram salt of wormwood are housed.Stirring heating refluxes nitrogen protection reaction 6 hours with 50ml toluene band water.After reaction is finished, except that desolvating, after separating purification, obtain the complete fragrant rigid annular prepolymer of chirality with underpressure distillation.Pure product are white powder.Productive rate is 90%.
Embodiment 11
Method such as embodiment ten all enlarge ten times with the reactant charging capacity, also can obtain chiral ring prepolymer.Productive rate is 91%.
Embodiment 12
Method such as embodiment ten add 5 gram salt of wormwood, also can obtain chiral ring prepolymer.Productive rate is 90.5%.
Embodiment 13
Method such as embodiment ten, solvent changes DMAC into, also can obtain chiral ring prepolymer.Productive rate is 89%.
Embodiment 14
Method such as embodiment ten, prolonging the reaction times is 24 hours, also can obtain chiral ring prepolymer.Productive rate is 91%.
Embodiment 15
Method such as embodiment ten replace with 3.67 gram (0.005mol) HOOC-BN-COOH with F-BN-F.Separate and purify, get the complete fragrant rigid annular prepolymer of chirality.Pure product are white powder.Productive rate is 90%.
Embodiment 16
Method such as embodiment 15 will react charging capacity and enlarge ten times, be dissolved in 1000mlDMF, also can obtain chiral ring prepolymer.Productive rate is 89%.
Embodiment 17
Method such as embodiment ten replace with 4 of 1.25 grams (0.005mol), 4 '-dihydroxy diphenylsulphone (bisphenol S) with Resorcinol.Separate and purify, get the complete fragrant rigid annular prepolymer of chirality.Pure product are white powder.Productive rate is 90%.
Embodiment 18
Method such as embodiment 15, Resorcinol replace with the bisphenol S of 1.25 grams (0.005mol).Get the complete fragrant rigid annular prepolymer of chirality.Pure product are white powder.Productive rate is 91%.
Embodiment 19
Method such as embodiment 15, prolonging the reaction times is 24 hours, also can obtain chiral ring prepolymer.Productive rate is 92%.
Claims (3)
1. the synthetic method of a chiral ring prepolymer, it is characterized in that: BN and 4,4 '-difluoro benzophenone or 4,4 '-benzophenonedicarboxylic acid, mol ratio is 1: 5-40, salt of wormwood is salt forming agent, joins in the organic polar solvent, under nitrogen protection, add 30-60ml toluene band water backflow 4-40 hour, underpressure distillation removes and desolvates then, obtains F-BN-F, HOOC-BN-COOH through separating to purify; Separate the chiral monomer that obtains opticity through common silicagel column; the monomeric mol ratio of F-BN-F or HOOC-BN-COOH and bisphenols 1: 1; salt of wormwood is salt forming agent; mix and add in the organic polar solvent; under nitrogen protection, reflux 4-40 hour, underpressure distillation removed and desolvates; obtain chiral ring prepolymer through separating to purify, productive rate is about 90%.
2. the synthetic method of chiral ring prepolymer as claimed in claim 1, it is characterized in that mol ratio is 1: 10-20, organic polar solvent are DMF, DMAC, band water return time is 8-12 hour, bisphenol compound is Resorcinol or '-biphenyl diphenol, dihydroxyphenyl propane, bisphenol S, tetramethyl biphenyl diphenol.
3. the synthetic method of chiral ring prepolymer as claimed in claim 1, it is characterized in that chiral monomer is dissolved in acetone, moving phase adopts hexanaphthene and acetone (acetone content is at 0-10%) to be separated into the dextrorotation chiral monomer, change moving phase into hexanaphthene and acetone (acetone content is 50-100%), stay the left-handed chiral monomer wash-out in post.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00102090 CN1108325C (en) | 2000-03-12 | 2000-03-12 | Synthesis of chiral ring prepolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00102090 CN1108325C (en) | 2000-03-12 | 2000-03-12 | Synthesis of chiral ring prepolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1263121A true CN1263121A (en) | 2000-08-16 |
| CN1108325C CN1108325C (en) | 2003-05-14 |
Family
ID=4576259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00102090 Expired - Fee Related CN1108325C (en) | 2000-03-12 | 2000-03-12 | Synthesis of chiral ring prepolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1108325C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002006195A1 (en) * | 2000-07-13 | 2002-01-24 | Merck Patent Gmbh | Chiral compounds ii |
-
2000
- 2000-03-12 CN CN 00102090 patent/CN1108325C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002006195A1 (en) * | 2000-07-13 | 2002-01-24 | Merck Patent Gmbh | Chiral compounds ii |
| US7318950B2 (en) | 2000-07-13 | 2008-01-15 | Merck Gmbh | Chiral compounds II |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1108325C (en) | 2003-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dietrich-Buchecker et al. | Interlocked and knotted rings in biology and chemistry | |
| Shahraki et al. | The flowering of mechanically interlocked molecules: Novel approaches to the synthesis of rotaxanes and catenanes | |
| Shen et al. | Difunctional paraquat dications (viologens) and their crown complexes: A new class of rotaxane monomers | |
| CN107880263B (en) | Temperature-responsive clustering peptide with side chain containing oligo-polyethylene glycol and preparation method thereof | |
| CN110407714A (en) | Hindered phenol and the compound difunctional antioxidant of amide groups intramolecular and its synthetic method | |
| CN113004521A (en) | Polysulfone and preparation method thereof | |
| CN102070775A (en) | Method for preparing multi-hydroxyl group-containing hyperbranched polyester resin | |
| CN114605640A (en) | High-performance polysulfone resin and preparation method and application thereof | |
| Pothanagandhi et al. | Chiral anion-triggered helical poly (ionic liquids) | |
| CN1108325C (en) | Synthesis of chiral ring prepolymer | |
| Xiong et al. | Tunable organic particles: An efficient approach from solvent-dependent Schiff base macrocycles | |
| CN109535062B (en) | Norbornene zwitterionic monomer and preparation method thereof | |
| CN111978537B (en) | Chiral catalyst (S) -DTP-COF, and preparation, recycling method and application thereof | |
| CN106832324A (en) | The preparation method of the cucurbit urea polymers with various topological structures | |
| CN102211973A (en) | Orientation-controllable benzophenanthrene disc-shaped liquid crystal molecule and preparation method thereof | |
| WO2023202060A1 (en) | Perylene-based micelle capable of rapidly adsorbing and efficiently degrading contaminant and method for preparing same | |
| CN108976434B (en) | Preparation method and application of eight-element cucurbituril-based super-molecular framework material | |
| CN102492737A (en) | Method for separating and purifying polyhydroxyalkanoate from interiors of microbial cells | |
| CN112604675B (en) | Preparation method and application of azobenzene dicarboxamide bridged beta-cyclodextrin chiral stationary phase | |
| CN1323846A (en) | Polycyanocryl ether and its prepn. method | |
| JP2003073349A (en) | Poly[3]rotaxane and method for producing the same | |
| CN106750538B (en) | A kind of polyoxomolybdate-polyethylene glycol hybrid and preparation method thereof | |
| CN114349672A (en) | Sulfydryl chlorothalonil and synthesis method, purification method and application thereof | |
| CN104860952B (en) | A kind of extraction separation method of high-purity cucurbit(7)uril | |
| CN1300104C (en) | Aryl monosulfur cyclic oligomer and its non-catalytic preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |