CN103293176B - A kind of method for determining chiral carboxylic acids optical purity - Google Patents
A kind of method for determining chiral carboxylic acids optical purity Download PDFInfo
- Publication number
- CN103293176B CN103293176B CN201310189223.2A CN201310189223A CN103293176B CN 103293176 B CN103293176 B CN 103293176B CN 201310189223 A CN201310189223 A CN 201310189223A CN 103293176 B CN103293176 B CN 103293176B
- Authority
- CN
- China
- Prior art keywords
- bis
- chiral
- deuterated
- nmr
- optical purity
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides a kind of method that utilization chiral chemistry shift reagen determines chiral carboxylic acids optical purity.With a series of chiral diamines such as 1,2 diphenyl ethylene diamines, cyclohexyl diamine, dinaphthalene diamines it is double（Sulphur）Urea derivative is chiral shift reagent, is used for quickly detecting using the optical purity of the chiral carboxylic acid of NMR.The synthesis of the method shift reagen is easy, simple to operate, be a kind of detection means rapidly and efficiently, convenient and practical.
Description
Technical field
Field the invention belongs to determine chipal compounds optical purity.The present invention is quickly to determine chiral carboxylic acids optical voidness
A kind of new method of degree.
Background technology
Chiral carboxylic acids are important construction units in natural products and drug molecule, are also important centre in organic synthesis
Body, therefore development is quick, facilitate, the method for the optical purity of Accurate Determining chiral carboxylic acids just becomes particularly important.Past
In decades, many methods for planting detection chiral carboxylic acids optical purity, such as high performance liquid chromatography, gas-chromatography have been developed
Method, capillary electrophoresis and nuclear magnetic resonance method etc..In these methods, it is using the nuclear magnetic resonance Split Method of chiral shift reagent
Chiral carboxylic acids optical purity one of the most quick and environment-friendly method is determined at present.The method is by chiral shift reagent
A pair of diastereomers are formed with the chiral carboxylic acids substrate of analysis, the difference of its chiral environment causes there is different chiral spies in substrate
The signal levied splits point.Each signal for splitting point correspond to a chiral carboxylic acids for configuration, as long as two split sub-signal peak
Chemical shift difference is wide enough so that on nuclear magnetic resoance spectrum being capable of baseline separation, then the enantiomeric purity of analysis substrate can
To be measured using nuclear-magnetism.The chiral chemistry shift reagen and carboxylic acid substrate of denier need to be only dissolved in deuterated solvent and existed by the method
Can be tested after being simply mixed in nuclear magnetic tube, except common NMR does not need other special equipment, with analysis
The outstanding advantage such as speed is fast, easy to operate, testing cost is cheap, so recent decades constantly have correlative study to report occur,
The polytype chiral shift reagent for chiral carboxylic acids analysis is had been developed at present（CSR）, such as amine, amino alcohol, diamines, acyl
Amine, macrocyclic compound, urea（Thiocarbamide）Class, but most all because carboxylic acid enantiomer Chiral properties1H chemical shifts
Difference is too small and baseline separation can not be realized, and a small number of Chemical shift differences are big, relatively effective to there is synthesis difficult or suitable
The problems such as using narrow range, therefore synthesize simple, convenient and practical, efficient chiral chemistry shift reagen and also need to further grind
Study carefully.
The content of the invention
It is an object of the invention to develop a kind of convenient and practical chiral chemistry shift reagen for chiral carboxylic acids optical voidness
Quick, the efficient detection of degree.
It is a feature of the present invention that with a series of with C2The chiral diamine of symmetry axis it is double（Sulphur）Urea derivative（Including 1,
[(the 3,5- bis trifluoromethyl phenyls of 2- bis-）Ghiourea group] -1,2- diphenylethanes, [(the 3,5- bis trifluoromethyl phenyls of 1,2- bis-）Urea
Base] -1,2- diphenylethanes, [(the 3,5- bis trifluoromethyl phenyls of 1,2- bis-）Ghiourea group]-hexamethylene, the [(3,5- double three of 1,2- bis-
Trifluoromethylphenyl）Urea groups]-hexamethylene, 2,2 '-two [(3,5- bis trifluoromethyl phenyls）Ghiourea group] -1,1 '-dinaphthalene, 2,2 '-two
[(3,5- bis trifluoromethyl phenyls）Urea groups] -1,1 '-dinaphthalene) it is chiral shift reagent, using the chiral carboxylic acid of NMR
Optical purity be used for quickly detecting.The present invention is developed with 1,2- diphenyl ethylene diamines, cyclohexyl diamine, dinaphthalene diamines first
It is double（Sulphur）The method that urea derivative detects chiral carboxylic acids optical purity by NMR, the synthesis of the method shift reagen
Easily, it is simple to operate, be a kind of detection means rapidly and efficiently, convenient and practical.
The allophanamide and bis-thiourea shift reagen that the present invention is used are characterised by：Represented by following chemical formula
The allophanamide and bis-thiourea chiral shift reagent that the present invention is used can be used alone or in pyridine, triethylamine, N, N-
Dimethyl -4-aminopyridine is used under doing auxiliary reagent.
Of the invention applied widely, rapidly and efficiently, favorable repeatability is convenient and practical, can be used for chiral carboxylic acids optical voidness
The high flux detection of degree.
The present invention is adopted the following technical scheme that:
1) racemic chiral carboxylic acids sample is dissolved in deuterated solvent, is put into NMR test, record it1H
NMR signal I.
2) a kind of chiral shift reagent used is dissolved in step 1）In deuterated solvent used, NMR survey is put into
Examination, records it1H NMR signals II.
3) racemic chiral carboxylic acids sample and chiral shift reagent are dissolved in step 1）In deuterated solvent used, in core
NMR test is put into after mixing in magnetic tube, it is recorded1H NMR signals III.
4) by any one optically pure chiral carboxylic acids sample（R or S types）Step 1 is dissolved in chiral shift reagent）Used
In deuterated solvent, NMR test is put into after mixing in nuclear magnetic tube, records it1H NMR signals IV.
5) will1H NMR signals III with1H NMR signals I and II are compareed, and determine the ownership of each signal peak, are found out chiral
The characteristic signal peak that shift reagen splits.
6) will1H NMR signals IV with1H NMR signals III is compareed, and determines to be split before and after separate characteristic signal peak in III
The absolute configuration of the corresponding carboxylic acid of two signals.
7) chiral carboxylic acids sample to be measured and chiral shift reagent are dissolved in step 1）In deuterated solvent used, in nuclear magnetic tube
NMR test is put into after middle mixing, it is recorded1H NMR signals V.To two groups of characteristic signals of corresponding carboxylic acid absolute configuration
Peak is integrated, and calculates the optical purity of testing sample.
Specific embodiment
The present invention is using 1,2- diphenyl ethylene diamines or the allophanamide of cyclohexyl diamine or dinaphthalene diamines（Or thiocarbamide）Derivative
Do chiral shift reagent and detected by NMR the optical purity of chiral carboxylic acids.
Certain density chiral carboxylic acids, chiral shift reagent, chiral carboxylic acids are tested respectively using NMR with chirality
Shift reagen mixture1H NMR.By three groups of check analysis1H NMR, find out and split by chiral shift reagent in biased sample
The chiral carboxylic acids characteristic signal peak opened is defined as target observation peak.NMR is recycled to test a kind of optical homochiral carboxylic acid
With chiral shift reagent mixture1H NMR, by compareing racemic chiral carboxylic acids with chiral shift reagent mixture1H
NMR, determines the absolute configuration of front and rear each corresponding chiral carboxylic acids of two groups of signals at target observation peak.
Chiral carboxylic acids sample to be measured and chiral shift reagent mixture are tested using NMR1H NMR.Target is seen
The absolute configuration for surveying the corresponding chiral carboxylic acids of larger signal at peak is the key component configuration of testing sample.It is exhausted to reaction carboxylic acid
To two groups of characteristic signal peaks integration of configuration, two differences of integral area are out with the business of two integral area sums and treat test sample
The optical purity of product.
It is for the chiral shift reagent that test process is used（R, R）[(the 3,5- bis trifluoromethyl phenyls of -1,2- two）Sulphur
Urea groups] -1,2- diphenylethanes or（R, R）[(the 3,5- bis trifluoromethyl phenyls of -1,2- two）Urea groups] -1,2- diphenylethanes or
（R, R）[(the 3,5- bis trifluoromethyl phenyls of -1,2- two）Ghiourea group]-hexamethylene or（R, R）[(the 3,5- bis trifluoromethyls of -1,2- two
Phenyl）Urea groups]-hexamethylene or [(the 3,5- bis trifluoromethyl phenyls of R-2,2 '-two）Ghiourea group] -1,1 '-dinaphthalene or R-2,2 '-two
[(3,5- bis trifluoromethyl phenyls）Urea groups] -1,1 '-dinaphthalene) or（S, S）[(the 3,5- bis trifluoromethyl phenyls of -1,2- two）Thiocarbamide
Base] -1,2- diphenylethanes or（S, S）[(the 3,5- bis trifluoromethyl phenyls of -1,2- two）Urea groups] -1,2- diphenylethanes or
（S, S）[(the 3,5- bis trifluoromethyl phenyls of -1,2- two）Ghiourea group]-hexamethylene or（S, S）[(the 3,5- bis trifluoromethyls of -1,2- two
Phenyl）Urea groups]-hexamethylene or [(the 3,5- bis trifluoromethyl phenyls of S-2,2 '-two）Ghiourea group] -1,1 '-dinaphthalene or S-2,2 '-two
[(3,5- bis trifluoromethyl phenyls）Urea groups] -1,1 '-dinaphthalene)；The chiral shift reagent for being used can be used alone or in pyrrole
Pyridine, triethylamine, N, N- dimethyl -4-aminopyridine are used under doing auxiliary reagent；The test carboxylic acid object being applicable have mandelic acid,
2- phenylpropionic acids, α-methoxyphenylacetic acid, alpha-brominated phenylacetic acid and other various chiral carboxylic acids containing α-H；Chiral shift is tried
Agent and carboxylic acid substrate can be tested in the concentration range of 1 mMol/L-15 mMol/L, and chiral shift reagent is with respect to carboxylic acid
Substrate can be used in the equivalent weight range of 0.1 equivalent -5；The deuterated solvent for being used can be deuterochloroform, deuterated benzene, deuterated
The single solvents such as tetrahydrofuran, deuterated toluene, deuterated dichloromethane or mixture, prioritizing selection deuterochloroform or deuterochloroform and
Deuterated benzol mixture；The NMR for using can be the instrument of 400 MHz, 500 MHz, 600 MHz and higher resolution,
Test temperature can be -50-50 DEG C.
Following with the case study on implementation specific description present invention.But the invention is not restricted to the form shown in case study on implementation,
Specific embodiment can carry out various changes in the range of specific embodiment of the invention explanation.
The measure of the optical purity of the mandelic acid mix-configuration sample of example 1
Take racemic mandelic acid, optical voidness R-MA, mandelic acid sample to be measured, N, N- dimethyl -4-aminopyridine, hand
Property shift reagen（S, S）[(the 3,5- bis trifluoromethyl phenyls of -1,2- two）Ghiourea group] -1,2- diphenylethanes are all made into 15
The chloroformic solution of deuteration of mMol/L is standby.The racemic mandelic acid chloroformic solution of deuteration for taking 0.2 mL preparations first adds 0.4 mL
Deuterochloroform, is put into the NMR of 400 MHz after being well mixed and records at room temperature1H NMR signals, with（δH= 0）
It is internal standard, the chemical shift for obtaining mandelic acid α-H is δ=5.26；Respectively take the racemic mandelic acid and N, N- bis- of 0.2 mL preparations
Methyl -4-aminopyridine, chiral shift reagent are put into the NMR of 400 MHz in room after adding same nuclear magnetic tube mixing
The lower record of temperature1H NMR signals, with（δH= 0）It is internal standard, obtains the chemical potential of the mandelic acid α-H after chiral shift reagent splits
It is δ to move1=5.159, δ2= 4.955；Respectively take 0.2 mL preparation optical voidness R-MA and N, N- dimethyl -4-aminopyridine,
Chiral shift reagent adds same nuclear magnetic tube to be put into the NMR of 400 MHz after mixing and records at room temperature1H NMR believe
Number, with（δH= 0）It is internal standard, the chemical shift for obtaining the mandelic acid α-H after chiral shift reagent splits is δ=4.955, with
This judges δ1=5.159 it is corresponding be S type mandelic acids, δ2=4.955 it is corresponding be R type mandelic acids.
The mandelic acid sample to be measured and N, N- dimethyl -4-aminopyridine, chiral shift reagent for respectively taking 0.2 mL preparations add
Enter to be put into the NMR of 400 MHz after same nuclear magnetic tube mixes and record at room temperature1H NMR signals, with（δH= 0）For
Internal standard, obtains chemical shift and the integral area of two groups of peak-to-peak signals of the mandelic acid α-H after splitting, and is δ1=5.159, S1 =
0.759, δ2=4.955, S2 = 0.200。δ1The component of S configurations in=5.159 larger explanation testing sample of signal peak area
It is on the high side, (S1-S2)/(S1+S2The optical purity of the explanation of)=0.58 testing sample is 58%.
The measure of the optical purity of the 2- phenylpropionic acid mix-configuration samples of example 2
Take racemic 2- phenylpropionic acids, optical voidness R-2- phenylpropionic acids, 2- phenylpropionic acids sample to be measured, N, N- dimethyl-
4-aminopyridine, chiral shift reagent（S, S）[(the 3,5- bis trifluoromethyl phenyls of -1,2- two）Ghiourea group] -1,2- diphenyl second
The chloroformic solution of deuteration that alkane is all made into 15 mMol/L is standby.The racemization 2- phenylpropionic acid deuterochloroforms of 0.2 mL preparations are taken first
Solution adds 0.4 mL deuterochloroforms, is put into after being well mixed in the NMR of 400 MHz and recorded at room temperature1H NMR
Signal, with（δH= 0）It is internal standard, obtains 2- phenylpropionic acids CH3The chemical shift of-H is δ=1.53；Respectively take 0.2 mL preparations
Racemic 2- phenylpropionic acids and N, N- dimethyl -4-aminopyridine, chiral shift reagent are put into after adding same nuclear magnetic tube mixing
Recorded at room temperature in the NMR of 400 MHz1H NMR signals, with（δH= 0）It is internal standard, obtains chiral shift reagent
2- phenylpropionic acids CH after fractionation3The chemical shift of-H is δ1=1.48, δ2= 1.44；Respectively take the optical voidness R- of 0.2 mL preparations
2- phenylpropionic acids and N, N- dimethyl -4-aminopyridine, chiral shift reagent are put into 400 MHz after adding same nuclear magnetic tube mixing
NMR in record at room temperature1H NMR signals, with（δH= 0）It is internal standard, after obtaining chiral shift reagent fractionation
2- phenylpropionic acids CH3The chemical shift of-H is δ=1.44, and δ is judged with this1=1.48 it is corresponding be S type 2- phenylpropionic acids, δ2=
1.44 it is corresponding be R type 2- phenylpropionic acids.
Respectively take 2- phenylpropionic acids sample to be measured and N, N- dimethyl -4-aminopyridine, the chiral shift examination of 0.2 mL preparations
Agent adds same nuclear magnetic tube to be put into the NMR of 400 MHz after mixing and records at room temperature1H NMR signals, with（δH =
0）It is internal standard, obtains the 2- phenylpropionic acids CH after splitting3The chemical shift of two groups of peak-to-peak signals of-H and integral area, are δ1=
1.48, S1 =1.200, δ2=1.44, S2 = 1.801。δ2R configurations in=1.44 larger explanation testing sample of signal peak area
Component it is on the high side, (S2-S1)/(S1+S2The optical purity of the explanation of)=0.20 testing sample is 20%.
Claims (6)
1. the assay method of chiral carboxylic acids optical purity, is examined using the optical purity of the chiral carboxylic acid of NMR
The step of survey, it is characterised in that：Use (R, R) -1,2- bis- [(3,5- bis trifluoromethyl phenyl) urea groups] -1,2- diphenylethanes
Or [(3,5- bis trifluoromethyl phenyl) urea groups] -1, the 2- diphenylethanes of (S, S) -1,2- bis- or (R, R) -1,2- bis- [(3,5- couples
Trifluoromethyl) urea groups]-hexamethylene or [(3,5- bis trifluoromethyl phenyl) the urea groups]-hexamethylenes of (S, S) -1,2- bis- or R-
2,2 '-two [(3,5- bis trifluoromethyl phenyls) urea groups] -1,1 '-dinaphthalenes or [(3,5- bis trifluoromethyl phenyls) ureas of S-2,2 '-two
Base] -1,1 '-dinaphthalene or [(3,5- bis trifluoromethyl phenyl) ghiourea group] -1, the 2- diphenylethanes of (R, R) -1,2- bis- or (S,
S) -1,2- bis- [(3,5- bis trifluoromethyl phenyl) ghiourea group] -1,2- diphenylethanes or (R, R) -1,2- bis- [(3,5- double three
Trifluoromethylphenyl) ghiourea group]-hexamethylene or [(3,5- bis trifluoromethyl phenyl) the ghiourea group]-hexamethylenes of (S, S) -1,2- bis- or
[(3,5- bis trifluoromethyl phenyls) ghiourea group]-the 1,1 '-dinaphthalenes of R-2,2 '-two or [(the 3,5- dual-trifluoromethyl benzenes of S-2,2 '-two
Base) ghiourea group] -1,1 '-dinaphthalene is chiral shift reagent, and chiral shift reagent and carboxylic acid substrate are 1mMol/L-15mMol/L's
Tested in concentration range, chiral shift reagent is used with respect to carboxylic acid substrate in the equivalent weight range of 0.1 equivalent -5.
2. assay method according to claim 1, it is characterised in that：The chiral shift reagent is used alone or in pyrrole
Pyridine, triethylamine, N, N- dimethyl -4-aminopyridine are used under doing auxiliary reagent.
3. assay method according to claim 1, it is characterised in that：The NMR be selected from 400MHz, 500MHz,
The instrument of 600MHz and higher resolution, test temperature is -50-50 DEG C.
4. assay method according to claim 1, it is characterised in that：In test process, the chiral shift reagent and institute
State carboxylic acid substrate and solution is configured to using deuterated solvent.
5. assay method according to claim 4, it is characterised in that：Deuterated solvent is selected from deuterochloroform, deuterated benzene, deuterated
Single solvent or mixture in tetrahydrofuran, deuterated toluene, deuterated dichloromethane.
6. assay method according to claim 5, it is characterised in that：Described deuterated solvent is selected from the deuterated chlorine of prioritizing selection
Imitative or deuterochloroform and deuterated benzol mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310189223.2A CN103293176B (en) | 2013-05-21 | 2013-05-21 | A kind of method for determining chiral carboxylic acids optical purity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310189223.2A CN103293176B (en) | 2013-05-21 | 2013-05-21 | A kind of method for determining chiral carboxylic acids optical purity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103293176A CN103293176A (en) | 2013-09-11 |
| CN103293176B true CN103293176B (en) | 2017-06-06 |
Family
ID=49094414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310189223.2A Expired - Fee Related CN103293176B (en) | 2013-05-21 | 2013-05-21 | A kind of method for determining chiral carboxylic acids optical purity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103293176B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ307419B6 (en) * | 2014-10-17 | 2018-08-08 | Vysoká škola chemicko-technologická v Praze | A method of determining the enantiomeric purity of chiral sulfoxides using 1 H-NMR analysis |
| JP6478188B2 (en) * | 2015-06-09 | 2019-03-06 | 国立研究開発法人物質・材料研究機構 | NMR chiral shifter and optical purity determination method using the same |
| CN106543058B (en) * | 2015-09-16 | 2019-09-20 | 中国科学院福建物质结构研究所 | A kind of chirality selenium carbamide compounds and its preparation and application |
| CN106018456A (en) * | 2016-05-16 | 2016-10-12 | 山东省分析测试中心 | Method for determining purity of daptomycin on basis of hydrogen nuclear magnetic resonance |
| CN108445033B (en) * | 2018-01-16 | 2020-01-31 | 温州大学 | Determination method for optical purity of alkaloids of 4- (3H) quinazolinone compounds |
| CN109293530A (en) * | 2018-11-12 | 2019-02-01 | 绍兴文理学院 | Chiral bisamide ester intermediate, chiral double urea ligands and the preparation method and application thereof |
| CN110261422A (en) * | 2019-05-16 | 2019-09-20 | 中国科学院福建物质结构研究所 | A kind of phosphorous chiral double applications of the porpezite metal complex in terms of chiral Recognition |
| CN110790665B (en) * | 2019-11-19 | 2021-06-18 | 中国科学院福建物质结构研究所 | Chiral titanium complex and preparation and application thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3915641A (en) * | 1971-11-03 | 1975-10-28 | Wisconsin Alumni Res Found | NMR method for determination of enantiomeric compositions with chiral shift reagents |
| KR0170925B1 (en) * | 1996-03-19 | 1999-05-01 | 강박광 | Method for measuring optical purity of organic compound using chiral amine by nmr |
| JP2001261613A (en) * | 2000-03-14 | 2001-09-26 | Tokyo Kasei Kogyo Kk | New optically-active magnetic-anisotropic reagent and method for determining optical purity and absolute configuration using the same |
| JP2003081911A (en) * | 2001-09-12 | 2003-03-19 | Tokyo Kasei Kogyo Kk | New optically active compound and method for determining excess amount of new eantiomer |
| JP2006028044A (en) * | 2004-07-13 | 2006-02-02 | T Hasegawa Co Ltd | Sugar compound useful as asymmetric induction reagent |
| WO2009113706A1 (en) * | 2008-03-11 | 2009-09-17 | 住友化学株式会社 | Method for discriminating polymer films |
| CN101550159B (en) * | 2009-05-13 | 2011-07-27 | 贵州大学 | A chiral bithioureido derivative containing phosphonate as well as its preparing method and use |
| JP5665043B2 (en) * | 2010-09-28 | 2015-02-04 | 独立行政法人物質・材料研究機構 | NMR chiral shifter and method for determining optical purity or absolute configuration using the same |
| CN102408344A (en) * | 2011-08-01 | 2012-04-11 | 温州大学 | Chiral solvating agents |
| CN102898465A (en) * | 2012-10-23 | 2013-01-30 | 中国科学院福建物质结构研究所 | Cyclohexanediamine-derived phosphamide chiral ligand as well as preparation method thereof and application thereof |
| CN103102280B (en) * | 2012-12-14 | 2016-09-14 | 中国科学院福建物质结构研究所 | The preparation method of optical voidness 1-(alpha-amido benzyl)-beta naphthal |
-
2013
- 2013-05-21 CN CN201310189223.2A patent/CN103293176B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103293176A (en) | 2013-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103293176B (en) | A kind of method for determining chiral carboxylic acids optical purity | |
| Bang et al. | Chiral recognition of (18-crown-6)-tetracarboxylic acid as a chiral selector determined by NMR spectroscopy | |
| Wenzel | Strategies for using NMR spectroscopy to determine absolute configuration | |
| Chaudhari et al. | Simple and efficient methods for discrimination of chiral diacids and chiral alpha-methyl amines | |
| Bai et al. | Enantiomeric NMR discrimination of carboxylic acids using actinomycin D as a chiral solvating agent | |
| Bozkurt et al. | New chiral oxo-bridged calix [2] arene [2] triazine for the enantiomeric recognition of α-racemic carboxylic acids | |
| CN102269744B (en) | Rapid detection method of residual amount of dimethylformamide in textiles | |
| Tanaka et al. | ‘Calixarene-like’chiral amine macrocycles as novel chiral shift reagents for carboxylic acids | |
| Li et al. | Enantiodiscrimination of carboxylic acids using the diphenylprolinol NMR chiral solvating agents | |
| Hassan et al. | Chiroptical sensing of amino acids, amines, amino alcohols, alcohols and terpenes with π-extended acyclic cucurbiturils | |
| González-Álvarez et al. | An azamacrocyclic receptor as efficient polytopic chiral solvating agent for carboxylic acids | |
| Liu et al. | Effective enantiomeric identification of aromatic amines by tyrosine-modified pillar [5] arenes as chiral NMR solvating agents | |
| De los Santos et al. | Chirality sensing with stereodynamic copper (I) complexes | |
| CN108752275B (en) | pH fluorescent probe and preparation method and application thereof | |
| Yuan et al. | A convenient synthesis of chiral dioxocyclens and application as chiral solvating agents | |
| CN107382935B (en) | A kind of coumarin fluorescent probe C1 and its preparation method and application | |
| Lovely et al. | Chiral NMR discrimination of amines: analysis of secondary, tertiary, and prochiral amines using (18‐crown‐6)‐2, 3, 11, 12‐tetracarboxylic acid | |
| Gao et al. | Enantiomeric discrimination of α-hydroxy acids and N-Ts-α-amino acids by 1H NMR spectroscopy | |
| Mishra et al. | A simple and rapid approach for testing enantiopurity of hydroxy acids and their derivatives using 1 H NMR spectroscopy | |
| Chen et al. | Stereospecific recognition of a chiral centre over multiple flexible covalent bonds by 19 F-NMR | |
| CN106543058B (en) | A kind of chirality selenium carbamide compounds and its preparation and application | |
| Yang et al. | Macrocyclic Compound as NMR chiral solvating agent for determination of enantiomeric excess of carboxylic acids | |
| Ulatowski et al. | Chiral Recognition of Carboxylates—Receptors, Analytical Tools, and More | |
| Barış et al. | Synthesis of rigid and C2-symmetric 18-crown-6 type macrocycles bearing diamide–diester groups: enantiomeric recognition for α-(1-naphthyl) ethylammonium perchlorate salts | |
| Li et al. | A Racemic Naphthyl‐Coumarin‐Based Probe for Quantitative Enantiomeric Excess Analysis of Amino Acids and Enantioselective Sensing of Amines and Amino Alcohols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170606 Termination date: 20210521 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |