CN106946838A - A kind of quick method for preparing the rhodamine with multiple labile functional groups under temperate condition - Google Patents
A kind of quick method for preparing the rhodamine with multiple labile functional groups under temperate condition Download PDFInfo
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- CN106946838A CN106946838A CN201710315490.8A CN201710315490A CN106946838A CN 106946838 A CN106946838 A CN 106946838A CN 201710315490 A CN201710315490 A CN 201710315490A CN 106946838 A CN106946838 A CN 106946838A
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- rhodamine
- alkyl
- functional groups
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- reduced pressure
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 36
- 125000000524 functional group Chemical group 0.000 title claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 62
- 229960000583 acetic acid Drugs 0.000 claims description 25
- 238000001556 precipitation Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000741 silica gel Substances 0.000 claims description 14
- 229910002027 silica gel Inorganic materials 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 239000012362 glacial acetic acid Substances 0.000 claims description 13
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- -1 sulfydryl Chemical group 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 4
- 125000001624 naphthyl group Chemical class 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000000090 biomarker Substances 0.000 abstract description 3
- 238000003384 imaging method Methods 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 3
- 239000000523 sample Substances 0.000 abstract description 3
- 238000007385 chemical modification Methods 0.000 abstract 1
- 238000001212 derivatisation Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- 239000000460 chlorine Substances 0.000 description 14
- 229960001866 silicon dioxide Drugs 0.000 description 13
- 239000013078 crystal Substances 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- ZMJPCIAEJKVKMQ-UHFFFAOYSA-M [4-[[4-[benzyl(methyl)amino]phenyl]-[4-(dimethylamino)phenyl]methylidene]cyclohexa-2,5-dien-1-ylidene]-dimethylazanium;chloride Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)CC=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 ZMJPCIAEJKVKMQ-UHFFFAOYSA-M 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 150000003935 benzaldehydes Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WFWZIRRKFGVIOS-UHFFFAOYSA-N 2-(2-bromoethoxy)benzaldehyde Chemical compound BrCCOC1=CC=CC=C1C=O WFWZIRRKFGVIOS-UHFFFAOYSA-N 0.000 description 1
- ZEDSAJWVTKUHHK-UHFFFAOYSA-N 2-ethynylbenzaldehyde Chemical compound O=CC1=CC=CC=C1C#C ZEDSAJWVTKUHHK-UHFFFAOYSA-N 0.000 description 1
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of quick method for preparing the rhodamine with multiple labile functional groups under temperate condition, it belongs to technical field of fine.This method has important directive significance by carrying out simple chemical modification to raw material and then synthesizing the rhodamine with particular functional group for the derivatization of rhodamine.Such rhodamine, with many active functional groups, is conducive to the derivative of rhodamine compared with commercially available.This method does not need the protection of inert gas; only need can just synthesize the rhodamine with particular functional group within 67 hours; the generated time of rhodamine is greatly saved, the purposes of rhodamine is expanded, the yield of rhodamine synthesis is greatly added.The separation for avoiding rhodamine is difficult.Above advantage has expanded the purposes of rhodamine, so that rhodamine can be in biomarker, cell imaging, the field such as fluorescence probe is sufficiently developed.
Description
Technical field
The present invention relates to a kind of quick method for preparing the rhodamine with multiple labile functional groups under temperate condition, its
Belong to technical field of fine.
Background technology
Application is widely in social production activity for rhodamine.For example, biomarker, cell imaging, glimmering
Light probe etc..Rhodamine is used to design fluorescence probe, heavy metal ion, harmful anion is effectively detected, while also may be used
For cell imaging, biomarker etc., but at the same time, the molecular structure of rhodamine is also complicated therewith, and this gives complex functionality
Rhodamine, which is brought, greatly to be challenged.Many steps are generally required using conventional method complex functionality rhodamine, while also existing
Intricately purification process.This causes rhodamine excellently photochemistry, Photophysics partite transport with being very restricted.Cause
This, in the urgent need to a kind of convenient, fast, method for efficiently synthesizing function rhodamine.
Conventional synthesis rhodamine method is usual under the high temperature conditions, strong acid；High temperature, ZnCl is dried by strict2；High temperature,
Reacted under strong acid, the exacting terms such as microwave.These methods obtain being the isomers of two kinds of extremely difficult separation, it is necessary to by preparation scale
The a small amount of multiple separation of high pressure liquid chromatography, therefore often price is prohibitively expensive for function rhodamine, using being extremely restricted.Work(
The synthesis of energy rhodamine mainly still uses prior synthesizing method at present, obtains the difficult isomers of two kinds of separation.One-step synthesis is not
There are only three kinds of methods that the function rhodamine of isomers is reported at present.First case is using acid anhydrides as raw material, at high temperature,
ZnCl2Catalysis two kinds of isomers of generation；Second case is the strong acid catalyst by raw material of aldehyde under microwave high-temperature, generates rhodamine；The
Three are first to prepare a cyclic ketones intermediate, then in strict anaerobic without under water, using grignard reagent or n-BuLi to urge
Agent generates rhodamine.(first case：M.Uddin L.J.Marnett, Org.lett, 2008,10,4799-4801；Second case：
G.Jiao, J.Castro, L.Thoresen, K.Burgess, Org.lett, 2003,5,3675-3677；3rd：Urano,
Y.；Kamiya,M.；Kanda,K.；Ueno,T.；Hirose,K.；Nagano,T.J.Am.Chem.Soc.2005,127,4888-
4894。
The content of the invention
From the foregoing, industry demand is capable of the method for invention Fast back-projection algorithm function rhodamine.To solve prior art
Present in problem, the present invention aims at the improvement bright method of high-temperature strong acid synthesizing rhodamine of the prior art, using than relatively low
Temperature and under conditions of organic acid makees solvent, to retain many highly active functional groups, so as to be conducive to rhodamine
Dyestuff is further used.The synthesizing rhodamine bright time can be shortened simultaneously, it is not necessary to the protection of inert gas, to simplify rhodamine
Dyestuff synthesis technique, in order to industrialize.
A kind of quick method for preparing the rhodamine with multiple labile functional groups under temperate condition, it is characterised in that：
The general structure of rhodamine with multiple labile functional groups is：
Wherein：R1Or R2Selected from H, C1-6Alkyl, (CH2CH2O)nH、(CH2)mCOOM or (CH2)mSO3M；R3Or R4Selected from H,
C1-6Alkyl, C1-6Alkyl-substituted phenyl, C1-6Alkyl-substituted naphthyl, halogen, OR6、N(R6)2、(CH2CH2O)nH、(CH2)mCOOM、(CH2)mSO3M, hydroxyl, sulfydryl, cyano group, nitro, heterocyclic radical, haloalkyl, alkyl amino, acylamino- and phenyl, simultaneously
Naphthyl, alkynyl, aldehyde radical；
N, m are respectively 1-6 integer；
M is H, K, Na, Li, NH4、NH3R5、NH2(R5)2、NH(R5)3Or N (R5)4。
This method comprises the following steps：
(1) it is (2~2.2) in molar ratio by substrate 1 and substrate 2:1 ratio is placed in two-mouth bottle, is added to toluene sulphur
Acid, adds glacial acetic acid or propionic acid, the p-methyl benzenesulfonic acid：The mol ratio of substrate 2 is (0.15~0.18):1；It is anti-at 70 DEG C
Answer 6-7 hours, glacial acetic acid is removed under reduced pressure, add saturation NaHCO3Solution, produces a large amount of bubbles, until precipitation precipitation, mistake completely
Filter precipitation, obtains rhodamine crude product；
(2) by rhodamine dissolving crude product in CH2Cl2Middle addition tetrachloroquinone, the tetrachloroquinone：Mole of substrate 2
Than for (0.5~0.6):1；Reaction 1~2 hour, is removed under reduced pressure CH2Cl2, silica gel post separation obtains rhodamine.
The substrate 1 can be selected from following compound：
The substrate 2 can be selected from following compound：
Described sour solvent is preferred：Acetic acid, propionic acid.The use of these sour advantages is that its is cheap, is readily obtained.Boiling point
It is relatively low, easily it can be removed by vacuum distillation.
Feed intake after end, add solvent, until solid material is completely dissolved.Then heat 6~7 hours, reaction solution is cold
But room temperature is arrived, solvent is boiled off.Add the sodium bicarbonate solution of saturation so that solution a large amount of bubbles occurs, while companion into alkalescent
With a large amount of precipitations of appearance.Precipitation is filtered out, and filter cake is preferably washed with deionized 3 times.After vacuum drying, dichloro is dissolved in
In methane, the tetrachloroquinone oxidation of 0.5 equivalent is added.
The reaction does not need the protection of inert gas, directly can carry out in atmosphere.
Preferably 6~7 hours, more preferably 7 hours reaction time.
After reaction terminates, solvent is boiled off.It is preferred that carrying out chromatographic column separating-purifying production as eluent with methylene chloride/methanol
Thing.Product is characterized by nuclear-magnetism and high resolution mass spectrum.
R1、R2、R3、R4, m, n, M compound as defined above in definition, R1、R2、R3、R4Because of different rhodamines dye
Material and it is different, using the alkyl chain of H or length not etc. to be excellent.
Further substrate 1 is 3- hydroxy-ns, and N- diethylanilines are excellent, using industrial raw material, cheap 100 yuan/
Acetone recrystallization before 500g uses, obtains colourless crystal.
By 1mmol aldehyde (substrate 2) and 2mmol 3- hydroxy-ns, N- diethylanilines are put in 25mL two-mouth bottle, plus
Enter 0.15mmol p-methyl benzenesulfonic acid, add 15mL glacial acetic acid.Under 70 degree react 6-7 hour, now solution become depth
Purple, depressurizes away most of acetic acid, adds the NaHCO of saturation3, a large amount of bubbles are produced, until purple precipitation was separated out completely
The precipitation of purple is filtered out, 30mL CH is dissolved in2Cl2Middle addition 0.5mmol tetrachloroquinone, the color of solution becomes deeper, instead
1-2h is answered, CH is removed under reduced pressure2Cl2, silica gel post separation obtains the crystal of brilliant violet color.Yield is more than 40%.
Required aldehyde can be reclaimed by separation well known in the art and purification technique, to reach the purity of needs.
The various raw materials used in the present invention are commercially available, or can be by the way that well known to a person skilled in the art method
Or disclosed method is simply prepared by raw material well known in the art in the prior art.
It should be understood that the various ring substituents in the compounds of this invention have some before above-mentioned steps progress or just complete
Cheng Hou, is introduced by the aromatics substitution reaction of standard or is produced by conventional modified with functional group, this is included in the present invention
Method and step in terms of.This reaction and modification include such as substituent by the introducing of aromatics substitution reaction, substituent also
The former, alkylation of substituent and the oxidation of substituent.Reagent and reaction condition for these processes are known to chemical field.
The instantiation of aromatics substitution reaction includes introducing nitro with concentrated nitric acid, is existed with such as carboxylic acid halides and lewis acid (such as alchlor)
Acyl group is introduced under the conditions of Friedel Crafts, with alkyl halide and lewis acid (such as alchlor) in Friedel Crafts bars
Alkyl is introduced under part, and introduces halogen group.The instantiation of modification is included for example, by carrying out catalytic hydrogenation with Raney nickel
Or heated in presence of hydrochloric acid with iron, nitro is reduced into amino；Alkylthio group is oxidized to alkyl sulphinyl
Or alkyl sulphonyl.
Unless otherwise indicated, term used herein has following meanings.
Term " alkyl " used herein includes straight chained alkyl and branched alkyl.As mentioned by single alkyl such as " propyl group ",
Straight chained alkyl is then only refered in particular to, then branched alkyl is only refered in particular to as mentioned by single branched alkyl such as " isopropyl ".For example, " C1-6Alkyl "
Including C1-4Alkyl, C1-3Alkyl, methyl, ethyl, n-propyl, isopropyl and the tert-butyl group.Similar rule is also applied for this explanation
The other groups used in book.Term " halogen " used herein includes fluorine, chlorine, bromine and iodine.
The beneficial effects of the invention are as follows：Isomers and photochemistry, light is not present in the rhodamine that this method synthesis is obtained
The excellent function rhodamine of physical property, such a method reacts single-minded, mild condition, and separating-purifying is simple, and yield is higher；It is suitable to
Reaction site can be efficiently controlled in the presence of multiple labile functional groups, obtains reacting single-minded function rhodamine.Synthesized in this
The innovation following points of method：
(1) raw material type range of choice is wide：The synthesis of rhodamine is needed from two kinds of compounds as raw material, this method pair
Regulation is can be carried out in two kinds of raw materials, this has just greatly widened the species for the rhodamine being synthesized, has added functionalization
Site.
(2) reaction condition is gentle：This method is less than 100 degree in reaction temperature, and reaction can be carried out under aerobic conditions, institute
With solvent, catalyst is cheap, it is easy to accomplish industrialization.
(3) reaction time is short：The bright method of the synthesizing rhodamine reported on document, even if being also required under the high temperature conditions very
In the long reaction time (being more than 24 hours), this method reaction time is short, it is easy to adjust, and can terminate reaction in 6-7 hours.
(4) reaction is easily handled：This method post processing is simple, it is easy to operates, works as pH>Product can just be analysed from solution when 7
Go out, simple filtering can be obtained by product.
(5) separate simple：This method separation is simple, does not deposit isomers, can be by recrystallizing, the method realization point such as extraction
From.
(6) react single-minded：This method reaction is single-minded, when containing multiple active functional groups, under certain condition, but
Single-minded obtains a certain required rhodamine, and other functional groups will not be destroyed.When active containing two or more in substrate
During functional group, it can effectively ensure that two active functional groups are not destroyed.When containing two aldehyde radicals in substrate, strict
Rate of charge is controlled, the product that only one of which aldehyde radical participates in reaction can be obtained, the selectivity of reaction is greatly improved.
(7) function rhodamine yield yield compared with conventional method that this method is obtained is higher, there is very big prospect.
Embodiment
The specific method of the synthesis of several function rhodamines is wherein also provided herein, but the method for patent covering is not
Only only include following several.
Embodiment 1
By p-bromobenzaldehyde (1mmol, 185mg) and 3- hydroxy-ns, N- diethylanilines (2mmol, 330mg) are put in 25mL
Two-mouth bottle in, add p-methyl benzenesulfonic acid (0.15mmol, 26mg), add 15mL glacial acetic acid.Reaction 7 is small under 70 degree
When, now solution becomes darkviolet, and most of acetic acid is removed under reduced pressure, and adds the NaHCO of saturation3, produce a large amount of bubbles, Zhi Daozi
Color precipitation separates out the precipitation for filtering out purple completely, is dissolved in 30mL CH2Cl2It is middle addition tetrachloroquinone (0.5mmol,
122mg), the color of solution becomes deeper, reacts 2h, CH is removed under reduced pressure2Cl2, silica gel post separation obtains the crystal of brilliant violet color.Production
Rate is 45%.1H NMR(400MHz,CDCl3):δ=7.79 (d, 2H, J=8.0Hz), 7.32-7.28 (m, 4H), 7.01-6.98
(m,2H),6.86(s,2H),3.72-3.66(t,8H),1.37-1.33ppm(m,12H).13C NMR(100MHz,CDCl3):δ
=158.1,157.8,131.2,130.9,125.2,114.5,113.3,93.8,44.5,12.9 ppm.ESI-HRMS
([C27H30N2OBr]+):calcd 477.1541,found 477.1545。
Embodiment 2
By 3-bromobenzaldehyde (1mmol, 185mg) and-hydroxy-n, N- diethylanilines (2mmol, 330mg) are put in 25mL
Two-mouth bottle in, add p-methyl benzenesulfonic acid (0.15mmol, 26mg), add 15mL glacial acetic acid.Reaction 7 is small under 70 degree
When, now solution becomes darkviolet, and most of acetic acid is removed under reduced pressure, and adds the NaHCO of saturation3, produce a large amount of bubbles, Zhi Daozi
Color precipitation separates out the precipitation for filtering out purple completely, is dissolved in 30mL CH2Cl2It is middle addition tetrachloroquinone (0.5mmol,
122mg), the color of solution becomes deeper, reacts 2h, CH is removed under reduced pressure2Cl2, silica gel post separation obtains the crystal of brilliant violet color.Production
Rate is 43%.1H NMR(400MHz,CDCl3):δ=7.78 (d, 1H, J=7.8Hz), 7.55-7.51 (t, 2H), 7.36 (d,
1H, J=7.6Hz), 7.30 (s, 1H), 7.05 (s, 1H), 6.97 (d, 2H, J=12.0Hz), 6.86 (s, 2H), 3.67-3.66
(m,8H),1.35-1.31ppm(t,12H).13C NMR(100MHz,CDCl3):δ=158.1,155.8,132.5,131.8,
131.2,125.1,114.5,113.3,97.0,46.4,12.9ppm.ESI-HRMS([C27H30N2OBr]+):
calcd.477.1541,found477.1547。
Embodiment 3
By 4-Fluorobenzaldehyde (1mmol, 124mg) and 3- hydroxy-ns, N- diethylanilines (2mmol, 330mg) are put in 25mL
Two-mouth bottle in, add p-methyl benzenesulfonic acid (0.15mmol, 26mg), add 15mL glacial acetic acid.Reaction 7 is small under 70 degree
When, now solution becomes darkviolet, and most of acetic acid is removed under reduced pressure, and adds the NaHCO of saturation3, produce a large amount of bubbles, Zhi Daozi
Color precipitation separates out the precipitation for filtering out purple completely, is dissolved in 30mL CH2Cl2It is middle addition tetrachloroquinone (0.5mmol,
122mg), the color of solution becomes deeper, reacts 2h, CH is removed under reduced pressure2Cl2, silica gel post separation obtains the crystal of brilliant violet color, produces
Rate is 41%.1H NMR(400MHz,CDCl3):δ=7.38 (d, 2H, J=4.0Hz), 7.33-7.31 (m, 4H), 6.98 (d,
2H, J=8.0Hz), 6.83 (s, 2H), 3.67-3.65 (m, 8H), 1.34-1.23ppm (m, 12H)13C NMR(100MHz,
CDCl3):δ=158.1,155.7,131.9,127.8,116.6,114.4,113.4,96.6,46.4,12.8 ppm.ESI-
HRMS([C27H30N2OF]+):calcd 417.2342,found 417.2343。
Embodiment 4
By 5- bromine water poplar formaldehyde (1mmol, 201mg) and 3- hydroxy-ns, N- diethylanilines (2mmol, 330mg) are put in
In 25mL two-mouth bottle, p-methyl benzenesulfonic acid (0.15mmol, 26mg) is added, 15mL glacial acetic acid is added.Reacted under 70 degree
7h, now solution become darkviolet, be removed under reduced pressure most of acetic acid, add the NaHCO of saturation3, produce a large amount of bubbles, Zhi Daozi
Color precipitation separates out the precipitation for filtering out purple completely, is dissolved in 30mL CH2Cl2It is middle addition tetrachloroquinone (0.5mmol,
122mg), the color of solution becomes deeper, reacts 2h, CH is removed under reduced pressure2Cl2, silica gel post separation obtains the crystal of brilliant violet color, produces
Rate is 44%.1H NMR(400MHz,CDCl3):δ=7.82 (d, 1H, J=12.0Hz), 7.47 (d, 3H, J=8.8Hz), 7.28
(s, 1H), 7.15 (s, 1H), 6.83-6.81 (d, 2H, J=8.0Hz), 6.69 (s, 2H), 3.60-3.55 (m, 8H), 1.31-
1.28(t,12H).13C NMR(100MHz,CDCl3):δ=158.1,155.8,155.1,134.0,133.6,132.0,
131.8,128.3,123.2,96.8,46.5,12.8ppm.ESI-HRMS([C27H30N2O2Br]+):calcd.493.1491,
found493.1473。
Embodiment 5
By paranitrobenzaldehyde (1mmol, 151mg) and 3- hydroxy-ns, N- diethylanilines (2mmol, 330mg) are put in
In 25mL two-mouth bottle, p-methyl benzenesulfonic acid (0.15mmol, 26mg) is added, 15mL glacial acetic acid is added.Reacted under 70 degree
7h, now solution become darkviolet, be removed under reduced pressure most of acetic acid, add the NaHCO of saturation3, produce a large amount of bubbles, Zhi Daozi
Color precipitation separates out the precipitation for filtering out purple completely, is dissolved in 30mL CH2Cl2It is middle addition tetrachloroquinone (0.5mmol,
122mg), the color of solution becomes deeper, reacts 2h, CH is removed under reduced pressure2Cl2, silica gel post separation obtains the crystal of purple, yield
For 43%.1H NMR(400MHz,CDCl3):δ=7.64 (d, 2H, J=8.0Hz), 7.50 (d, 2H, J=7.6Hz), 7.18 (d,
2H, J=8.4Hz), 6.89 (d, 2H, J=7.6Hz), 6.73 (s, 2H), 3.63-3.61 (m, 8H), 1.36-1.25ppm (m,
12H).13C NMR(100MHz,CDCl3):δ=158.0,155.9,153.9,149.1,138.6,131.4,131.0,124.4,
115.1,113.1,97.1,46.6,12.9ppm.ESI-HRMS([C27H30N3O3]+):calcd 444.2287,
found444.2284。
Embodiment 6
25mL will be put in two benzaldehydes (1mmol, 134mg) and 3- hydroxy-ns, N- diethylanilines (2mmol, 330mg)
Two-mouth bottle in, add p-methyl benzenesulfonic acid (0.15mmol, 26mg), add 15mL glacial acetic acid.Under 70 degree reaction 6~
7h, now solution become darkviolet, be removed under reduced pressure most of acetic acid, add the NaHCO of saturation3, produce a large amount of bubbles, Zhi Daozi
Color precipitation separates out the precipitation for filtering out purple completely, is dissolved in 30mL CH2Cl2It is middle addition tetrachloroquinone (0.5mmol,
122mg), the color of solution becomes deeper, reacts 2h, CH is removed under reduced pressure2Cl2, silica gel post separation obtains the crystal of purple, yield
For 40%.1H NMR(400MHz,CDCl3):δ=10.18 (s, 1H), 8.17 (d, 2H, J=8.0Hz), 7.60 (d, 2H, J=
7.6Hz), 7.25 (d, 2H, J=12.0Hz), 6.98 (d, 2H, J=12.0Hz), 6.85 (s, 2H), 3.68-3.64 (m, 8H),
1.34-1.31ppm(t,12H).13C NMR(100MHz,CDCl3):δ=191.7,158.0,155.8,155.4,137.9,
137.5,131.7,114.7,113.1,96.8,94.6,46.5,12.9ppm.ESI-HRMS([C28H31N2O2]+):
calcd.427.2386；found 427.2394.
Embodiment 7
Parahydroxyben-zaldehyde (2mmol, 244mg) is dissolved in 20ml DMF, K is added2CO3(20mmol, 26g), is stirred
5min is mixed so that parahydroxyben-zaldehyde dissolves, addition 1,2- Bromofumes (20mmol, 36g) react 3h under 70 degree, depressurize out
Substantial amounts of DMF is removed, a small amount of DMF is poured into trash ice and separates out flaxen solid, is filtered, next step reaction is directly carried out.
By bromoethoxy benzaldehyde (1mmol, 228mg) and 3- hydroxy-ns, N- diethylanilines (2mmol, 330mg) are put
In 25mL two-mouth bottle, p-methyl benzenesulfonic acid (0.15mmol, 26mg) is added, 15mL glacial acetic acid is added.It is anti-under 70 degree
Answer 6~7 hours, now solution becomes darkviolet, most of acetic acid is removed under reduced pressure, add the NaHCO of saturation3, produce a large amount of gas
Bubble, separates out the precipitation for filtering out purple until purple is precipitated, is dissolved in 30mL CH completely2Cl2Middle addition tetrachloroquinone
(0.5mmol, 122mg), the color of solution becomes deeper, reacts 2 hours, CH is removed under reduced pressure2Cl2, silica gel post separation obtains purple
The crystal of color, yield 50%.1H NMR(400MHz,CDCl3):δ=7.46 (d, 2H, J=12.0Hz), 7.36 (d, 2H, J=
8.0Hz), 7.21 (d, 2H, J=7.6Hz), 6.97 (d, 2H, J=8.0Hz), 6.80 (s, 2H), 4.50-4.42 (m, 2H),
3.95 (d, 1H, J=4.0Hz), 3.78-3.75 (t, 1H), 3.69-3.63 (t, 8H), 1.34-1.32ppm (t, 12H)13C
NMR(100MHz,CDCl3):δ=160.2,158.1,157.6,155.5,132.4,131.6,124.4,115.4,114.3,
113.5,96.6,68.6,46.3,42.3,12.9ppm.MALDI-HRMS([C29H34N2O2Br]+):calcd.521.1804,
found 521.1774。
Embodiment 8
P-bromobenzaldehyde (2mmol, 370mg) is dissolved in 15ml anhydrous triethylamine, vacuumized, three are replaced with argon gas
It is secondary, weigh Pd (PPh3)2Cl2(0.06mmol, 43mg), PPh3(0.06mmol, 16mg), CuI (0.02mmol, 4mg) is added.
It is then injected into 0.5ml trimethylsilyl acetylene.70 degree are heated to, reacts 6 hours, is cooled to after room temperature, consolidating for white is filtered out
Body, uses CH2Cl2Repeatedly wash filter cake.Removal of solvent under reduced pressure.Cross silicagel column.Then obtained brown solid is dissolved in methanol
In, add K2CO3(2mmol, 390mg) is reacted at room temperature 3 hours, filters K2CO3, pressurize and remove methanol, cross silicagel column, leacheate
For petroleum ether：Dichloromethane (1:1) 195mg, is obtained, yield is 75%.
Ethynylbenzaldehyde (1mmol, 130mg) and 3- hydroxy-ns, N- diethylanilines (2mmol, 330mg) will be put in
In 25mL two-mouth bottle, p-methyl benzenesulfonic acid (0.15mmol, 26mg) is added, 15mL glacial acetic acid is added.6 are reacted under 70 degree
~7 hours, now solution became darkviolet, and most of acetic acid is removed under reduced pressure, and added the NaHCO of saturation3, a large amount of bubbles are produced,
The precipitation for filtering out purple is separated out completely until purple is precipitated, and is dissolved in 30mL CH2Cl2It is middle addition tetrachloroquinone (0.5mmol,
122mg), the color of solution becomes deeper, reacts 2 hours, CH is removed under reduced pressure2Cl2, silica gel post separation obtains the crystal of purple,
Yield is 36%.1H NMR(400MHz,CDCl3):δ=7.78-7.72 (m, 2H), 7.38-7.30 (m, 4H), 6.98-6.93
(m, 2H), 6.89 (d, 2H, J=4.0Hz), 3.70-3.65 (m, 8H), 3.27 (s, 1H), 1.36-1.32 (t, 12H) ppm.13C
NMR(100MHz,CDCl3):δ=12.6,46.5,96.9,113.3,114.5,125.0,129.7,131.2,131.9,
132.5,132.8,155.7,158.1ppm.ESI-HRMS([C29H31N2O]+):calcd.423.2436,found
423.2432。
Will be to 4- (2- nitrine base oxethyl) benzaldehydes (1mmol, 160mg) and 3- hydroxy-ns, N- diethylanilines
(2mmol, 330mg) is put in 25mL two-mouth bottle, adds p-methyl benzenesulfonic acid (0.15mmol, 26mg), adds 15mL ice
Acetic acid.Reacted 7 hours under 70 degree, now solution becomes darkviolet, most of acetic acid is removed under reduced pressure, add saturation
NaHCO3, a large amount of bubbles are produced, the precipitation for filtering out purple is separated out completely until purple is precipitated, is dissolved in 30mL CH2Cl2In
Tetrachloroquinone (0.5mmol, 122mg) is added, the color of solution becomes deeper, react 2 hours, CH is removed under reduced pressure2Cl2, silicagel column
Separation, obtains the crystal of purple, yield is 55%.1H NMR(400MHz,CDCl3):δ=7.43 (d, 2H, J=12.0Hz),
7.32 (d, 2H, J=8.0Hz), 7.18 (d, 2H, J=7.6Hz), 6.94-6.91 (m, 2H), 6.78 (s, 2H), 4.32-4.29
(m,2H),3.69-3.67(t,2H),3.65-3.59(m,8H),1.31-1.28ppm(t,12H).13C NMR(100MHz,
CDCl3):δ=160.0,157.8,157.3,155.2,132.1,131.2,124.0,115.1,114.0,11 3.1,96.2,
67.4,50.1,46.0,12.6ppm.ESI-HRMS([C29H34N5O2]+):calcd.484.2713,found 487.2710。
Claims (1)
1. a kind of quick method for preparing the rhodamine with multiple labile functional groups under temperate condition, it is characterised in that：Band
The general structure of the rhodamine of multiple labile functional groups is：
Wherein：R1Or R2Selected from H, C1-6Alkyl, (CH2CH2O)nH、(CH2)mCOOM or (CH2)mSO3M；
R3Or R4Selected from H, C1-6Alkyl, C1-6Alkyl-substituted phenyl, C1-6Alkyl-substituted naphthyl, halogen, OR6、N(R6)2、
(CH2CH2O)nH、(CH2)mCOOM、(CH2)mSO3M, hydroxyl, sulfydryl, cyano group, nitro, heterocyclic radical, haloalkyl, alkyl amino,
Acylamino- and phenyl and naphthyl, alkynyl, aldehyde radical；
M is H, K, Na, Li, NH4、NH3R5、NH2(R5)2、NH(R5)3Or N (R5)4, R5For H, C1-6Alkyl or CH2CH2OH；
R6For H, C1-6Alkyl, (CH2CH2O)nH、(CH2)mCOOM、(CH2)mX or (CH2)mSO3M；X is F, Cl, Br or I；
N, m are respectively 1-6 integer；
This method comprises the following steps：
（1）It is in molar ratio by substrate 1 and substrate 2 (2 ~ 2.2):1 ratio is placed in two-mouth bottle, adds p-methyl benzenesulfonic acid, then
Add glacial acetic acid or propionic acid, the p-methyl benzenesulfonic acid：The mol ratio of substrate 2 is (0.15 ~ 0.18):1；
70oReacted 6-7 hours under C, glacial acetic acid is removed under reduced pressure, add saturation NaHCO3Solution, produces a large amount of bubbles, Zhi Daochen
Form sediment and separate out completely, filtering precipitation obtains rhodamine crude product；
（2）By rhodamine dissolving crude product in CH2Cl2Middle addition tetrachloroquinone, the tetrachloroquinone：The mol ratio of substrate 2 is
（0.5~0.6）:1；Reaction 1 ~ 2 hour, is removed under reduced pressure CH2Cl2, silica gel post separation obtains rhodamine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111763190A (en) * | 2019-04-02 | 2020-10-13 | 湖北华大基因研究院 | Synthesis method and application of dichloro rhodamine dye |
| USRE49362E1 (en) | 2006-05-18 | 2023-01-10 | Illumina Cambridge Limited | Dye compounds and the use of their labelled conjugates |
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| DE102008043765A1 (en) * | 2008-11-14 | 2010-05-27 | Julius-Maximilians-Universität Würzburg | Preparing dye in liquid comprises contacting liquid with educt, heating liquid in microwave oven, and cooling the liquid, where the production of the dye is spectroscopically monitored by means of a spectroscopic sensor in real time manner |
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| DE102008043765A1 (en) * | 2008-11-14 | 2010-05-27 | Julius-Maximilians-Universität Würzburg | Preparing dye in liquid comprises contacting liquid with educt, heating liquid in microwave oven, and cooling the liquid, where the production of the dye is spectroscopically monitored by means of a spectroscopic sensor in real time manner |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE49362E1 (en) | 2006-05-18 | 2023-01-10 | Illumina Cambridge Limited | Dye compounds and the use of their labelled conjugates |
| CN111763190A (en) * | 2019-04-02 | 2020-10-13 | 湖北华大基因研究院 | Synthesis method and application of dichloro rhodamine dye |
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