CS196694B1 - Process for preparing polymere aromatic amines - Google Patents
Process for preparing polymere aromatic amines Download PDFInfo
- Publication number
- CS196694B1 CS196694B1 CS159377A CS159377A CS196694B1 CS 196694 B1 CS196694 B1 CS 196694B1 CS 159377 A CS159377 A CS 159377A CS 159377 A CS159377 A CS 159377A CS 196694 B1 CS196694 B1 CS 196694B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- coupled
- nitrite
- reaction
- polymer
- diazotized
- Prior art date
Links
- 150000004982 aromatic amines Chemical class 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 229920000642 polymer Polymers 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 3
- OZJYQRCHIJUTOX-UHFFFAOYSA-N N(=O)O.OCCC=C(C(=O)O)C Chemical compound N(=O)O.OCCC=C(C(=O)O)C OZJYQRCHIJUTOX-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000987 azo dye Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000006193 diazotization reaction Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims 2
- 239000012528 membrane Substances 0.000 claims 2
- 102000016938 Catalase Human genes 0.000 claims 1
- 108010053835 Catalase Proteins 0.000 claims 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims 1
- 108010015776 Glucose oxidase Proteins 0.000 claims 1
- 239000004366 Glucose oxidase Substances 0.000 claims 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000002255 enzymatic effect Effects 0.000 claims 1
- 239000008103 glucose Substances 0.000 claims 1
- 229940116332 glucose oxidase Drugs 0.000 claims 1
- 235000019420 glucose oxidase Nutrition 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- UWPJYQYRSWYIGZ-UHFFFAOYSA-N 5-aminonaphthalene-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2C(N)=CC=CC2=C1 UWPJYQYRSWYIGZ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Je známa reakce mezi nízkomolekulárními organickými dusitany a různými reaktivními látkami; v polymerní oblasti nebylo však této reakce k praktickým účelům dosud použito. Důvodem může být skutečnost, že nebyla dosud známa vhodná polymerní látka, která by tuto přípravu umožnila, ačkoliv z mnoha důvodů vzniklý polymerní amin může mír řadu prakticky využitelných vlastností.The reaction between low molecular weight organic nitrites and various reactive substances is known; however, in the polymeric field this reaction has not yet been used for practical purposes. This may be due to the fact that a suitable polymeric substance to enable this preparation has not been known yet, although for many reasons the polymer amine formed can have a number of practically useful properties.
Reakce mezi polymerním dusitanem 2-hydroxyethylmethakrylátu (připraveným podle autorského osvědčení č. 195 942) a nízkomolekulárním aromatickým aminem, resp. diaminem může být s výhodou použita pro vazbu aromatické aminoskupiny na tento polymerní nosič. Vzniklý modifikovaný polymer lze použít přímo jako slabě bazický chromatografický materiál, ať již do kolon, nebo pro přípravu tenkých vrstev. V analytické praxi a při nejrůznějších chemických a biochemických separačních technikách může být významná skutečnost, že navázaný primární aromatický amin je možno diazotovat a následující kopulací za velmi mírných (fyziologických) podmínek immobilizovat citlivé látky kovalentní vazbou na polymerní nosič.Reaction between polymeric nitrite of 2-hydroxyethyl methacrylate (prepared according to the author's certificate No. 195 942) and low molecular weight aromatic amine, respectively. The diamine may advantageously be used to bind an aromatic amino group to the polymeric carrier. The resulting modified polymer can be used directly as a weakly basic chromatographic material, either in columns or for thin film preparation. In analytical practice and in a variety of chemical and biochemical separation techniques, it may be significant that the attached primary aromatic amine can be diazotized and, by subsequent coupling under very mild (physiological) conditions, immobilize sensitive substances by covalent bonding to a polymeric carrier.
Reakce dusitanu poly(2-hydroxyethyl-methakrylátu) s aromatickými aminy představuje tedy další z možností chemické modifikace příslušného polymeru.The reaction of poly (2-hydroxyethyl methacrylate) nitrite with aromatic amines thus represents another possibility of chemical modification of the polymer.
Předmětem vynálezu je způsob výroby polymerních aromatických aminů, při kterém se aromatický amin nebo diamin nechá reagovat s dusitanem poly(2-hydroxyethyl-methakrylátu) v bezvodém prostředí při teplotě 55 až 150 °C. Reakci lze s výhodou provádět v přítomnosti rozpouštědla, ve kterém jak výchozí polymerní dusitan, taki reakční produkt botná alespoň ze 2 %. S výhodou se používá například 1,4-dioxan, aceton nebo dimethylformamid. Reakční doba se s výhodou pohybuje od 1 minuty do 2 hodin; záleží na požadovaném stupni konverse a na teplotě při alkylační reakci. Popřípadě nezreagované skupiny esteru dusitanu lze převést na původní hydroxylové skupiny velmi snadno hydrolysou vodou, popřídadě urychlenou ohřevem. Je důležité, že v případě následující diazotace je vzniklá diazoniová sůl polymeru stálejší, než dusitan opět vznikající esterifikací zbývajících hydroxylových skupin polymeru; umožní to totiž rozložit ester např. 1 N HC1 při 25 °C a eliminovat tak možnost vzniku nitrosních plynů během případné následující kopulace (významné zejména pro vazbu citlivých a biologicky aktivních molekul).SUMMARY OF THE INVENTION The present invention provides a process for the preparation of polymeric aromatic amines, wherein the aromatic amine or diamine is reacted with poly (2-hydroxyethyl methacrylate) nitrite in an anhydrous environment at a temperature of 55 to 150 ° C. The reaction may preferably be carried out in the presence of a solvent in which both the starting polymer nitrite and the reaction product swell at least 2%. For example, 1,4-dioxane, acetone or dimethylformamide is preferably used. The reaction time is preferably from 1 minute to 2 hours; it depends on the desired degree of conversion and the temperature of the alkylation reaction. The optionally unreacted nitrite ester groups can be converted to the original hydroxyl groups very easily by hydrolysis with water, possibly accelerated by heating. Importantly, in the case of subsequent diazotization, the resulting diazonium salt of the polymer is more stable than the nitrite formed by esterification of the remaining hydroxyl groups of the polymer; this makes it possible to decompose the ester, for example, with 1 N HCl at 25 ° C, thus eliminating the possibility of nitrous gases during possible subsequent coupling (particularly important for the binding of sensitive and biologically active molecules).
V následujícím je předmět vynálezu blíže objasněn na několika příkladech použití.In the following, the invention is explained in more detail by means of several examples of use.
Příklad 1Example 1
Byl připraven polymerní dusitan esterifikací poly(2-hydro-xyetliyl-methakrylátu) kyselinou dusitou (podle autorského osvědčení 195 942), materiál však nebyl sušen, ale převeden do 1,4-dioxanu, pak vhozen do vroucího 5% p-nitranilinu v 1,4dioxanu a zahříván k varu 1 hodinu. Červenohnědě zbarvený produkt byl pak redukován varem ve směsi 10% HCl (35 % p. a. preparát), 40% H2O dest. a 50 % dioxanu s přídavkem 6% SnCl2 p. a. Během asi 2 minut zmizí červené zabarvení (redukce nitrosaminu), za 15 minut zmizí i žlutá barva redukcí nitroskupiny. Vzniklý na polymer vázaný p-fenylendiamin byl pak diazotován 25% vodným roztokem kyseliny octové s přídavkem 1 % NaNO2 při 0 °C, přechodně vzniklý dusitan byl rozloženIt was prepared by polymeric nitrite by esterification of poly (2-hydroxyethyl-methacrylate) with nitrous acid (according to author's certificate 195 942), but the material was not dried but transferred to 1,4-dioxane then thrown into boiling 5% p-nitraniline in 1 , 4-dioxane and heated to boiling for 1 hour. The red-brown colored product was then reduced by boiling in a mixture of 10% HCl (35% pa preparation), 40% H 2 O dest. and 50% dioxane with the addition of 6% SnCl 2 pa In about 2 minutes the red color disappears (nitrosamine reduction), and in 15 minutes the yellow color also disappears by reduction of the nitro group. The resulting polymer-bound p-phenylenediamine was then diazotized with 25% aqueous acetic acid with the addition of 1% NaNO 2 at 0 ° C, the transient nitrite was decomposed
3,5 % HCl při 25 °C a polymer kopulován v neutrálním pH s kyselinou Cléveovou (l-naftylamin-6sulfonová). Vzniklé azobarvivo, vázané na polymer, způsobuje jeho modrofialovou (kyselé prostředí), resp. hnědou (bazické prostředí) barvu.3.5% HCl at 25 ° C and the polymer coupled at neutral pH with Cléveic acid (1-naphthylamine-6sulfonic acid). The resulting azo dye bound to the polymer causes its blue-violet (acidic) environment, respectively. brown (basic) color.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS159377A CS196694B1 (en) | 1977-03-09 | 1977-03-09 | Process for preparing polymere aromatic amines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS159377A CS196694B1 (en) | 1977-03-09 | 1977-03-09 | Process for preparing polymere aromatic amines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS196694B1 true CS196694B1 (en) | 1980-03-31 |
Family
ID=5350697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS159377A CS196694B1 (en) | 1977-03-09 | 1977-03-09 | Process for preparing polymere aromatic amines |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS196694B1 (en) |
-
1977
- 1977-03-09 CS CS159377A patent/CS196694B1/en unknown
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Vita et al. | Scorpion toxins as natural scaffolds for protein engineering. | |
| Danielli | Studies on the cytochemistry of proteins | |
| CN113789366B (en) | CRISPR/Cas-driven DNA hydrogel colorimetric sensor and its preparation method and application | |
| DE2708018C2 (en) | ||
| CS196694B1 (en) | Process for preparing polymere aromatic amines | |
| Boyd et al. | N‐ACYLSUCCINIMIDES AS ACYLATING AGENTS FOR PROTEINS: THE SELECTIVE ACYLATION OF LYSINE RESIDUES | |
| Lillehaug et al. | Reaction of biological thiols with the tumor inhibitor of jatrophone Inhibition of RNA polymerase | |
| JPH05504672A (en) | Polynucleotide probes, methods and kits for the identification and detection of Gram-negative bacteria | |
| Behr | Photohydrolysis of DNA by polyaminobenzenediazonium salts | |
| Ohta et al. | Structural Fluctuation of the Polypeptide‐Chain Elongation Factor Tu: A Comparison of Factors from Escherichia coli and Thermus thermophilus HB8 | |
| Küchler et al. | Preparation and Applications of Dendronized Polymer–Enzyme Conjugates | |
| Rusin et al. | Novel water-soluble porphyrin-based receptors for saccharide recognition | |
| Ghosh et al. | Design and synthesis of anthracene-based bispyridinium amides: anion binding, cell staining and DNA interaction studies | |
| DE1467782A1 (en) | Process for the production of artificial antigens | |
| US6582952B1 (en) | Method for eliminating a nitrogenated heterocyclic, or aromatic, compound in an effluent | |
| Nakajima et al. | Polymerization of L-Alanylglycine with Diphenylphosphoryl Azide | |
| CH626402A5 (en) | Process for immobilising proteins on a solid support | |
| SU586182A1 (en) | Method of preparing immobilized a-amylase | |
| CN102181068A (en) | Polyurethane material subjected to photo-induced graft surface modification by fungi polysaccharide and preparation method thereof | |
| Schäfer et al. | Synthesis and properties of 8-azido-1, N6-etheno adenosine triphosphate—a fluorescent and photosensitive ATP analog | |
| CN115340530B (en) | Method for preparing nitrogen-containing heterocyclic derivative and application thereof | |
| SU1052509A1 (en) | Method for preparing sorbent for immobilizing biologically active substances | |
| Diopoh et al. | New Protein Reagents. N‐(4‐Chloromercuriphenyl)‐4‐Chloro‐3, 5‐Dinitrobenzamide and Its Use as a Probe of the Quaternary Structure of Yeast Alcohol Dehydrogenase | |
| SU767120A1 (en) | Method of preparing modified enzymes | |
| Karim et al. | Formation of protein conjugates of phosphorothioate nucleoside diphosphate beta-S |