Low-temperature reactive aryl azides

Abstract

The present invention relates to a compound of formula (I), wherein R1 is selected from the group consisting of B1 and Y1, R2 is selected from the group consisting of B2 and Y2, R3 is selected from the group consisting of B3 and Y3, and R4 is selected from the group consisting of B4 and Y4; and B1 and B3 are independently selected from the group consisting of fluoro, chloro and bromo; B2 and B4 are independently selected from the group consisting of hydrogen and fluoro; when R1 is Y1 and R2 is Y2, Y1 is selected from the group consisting of oxygen, sulfur and selenium, and Y2 is -CH2CH2- or -CH=CH-, and together with Y1 forms a five-membered ring system; when R3 is Y3 and R4 is Y4, Y3 is selected from the group consisting of oxygen, sulfur and selenium, and Y4 is -CH2CH2- or -CH=CH-, and together with Y3 forms a five-membered ring system; and X is D-(L p -A) m H 1-m The formula is selected from the group consisting of S and O, where D is selected from the group consisting of S and O, p is 1, m is 1, L is a linker group, and A is a reactive group. JPEG2026521068000033.jpg60166

Claims

1. Compound of formula I: 【Chemistry 1】 During the ceremony, R １ B １ and Y １ Selected from the group consisting of, R ２ B ２ and Y ２ Selected from the group consisting of, R ３ is selected from the group consisting of B ３ and Y ３ and is selected from the group consisting of R ４ B ４ and Y ４ Selected from the group consisting of, B １ and B ３ These are independently selected from the group consisting of fluoro, chloro, and bromo, B ２ and B ４ These are independently selected from the group consisting of hydrogen and fluoro, R １ Y １ And R ２ Y ２ When Y １ is selected from the group consisting of oxygen, sulfur, and selenium, and Y ２ is, -CH ２ CH ２ - or -CH = CH-, Y １ Together with it, it forms a five-membered ring system, R ３ Y ３ And R ４ Y ４ When Y ３ is selected from the group consisting of oxygen, sulfur, and selenium, and Y ４ is, -CH ２ CH ２ - or -CH = CH-, Y ３ Together with it, it forms a five-membered ring system, X is D - (L ｐ -A) ｍ H １－ｍ Selected from the group consisting of, Here, D is selected from the group consisting of S and O. p is 1 and m is 1, L is an alkylene chain having 1 to 18 carbon atoms, an alkenyl chain having 1 to 18 carbon atoms, an alkynyl chain having 1 to 18 carbon atoms, an oligoethylene oxide having 2 to 10 repeating units, or an oligo-C having 2 to 10 repeating units. １ ~C ５ - Alkyloxazoline, oligo-C having 2 to 10 repeating units １ ~C ５ - A linker group selected from the group consisting of alkyl oxazines, peptide chains, polydimethylsiloxanes, perfluoroethers, perfluoroalkyls, polyisobutenes, polyethylene glycols, polydimethylacrylamides, polyvinylpyrrolidones, polyalkyloxazolines, polyalkyloxazines, dextran, carboxymethyl dextran, poly(N-isopropylacrylamide), poly(N-hydroxyethylacrylamide), poly(2-hydroxyethyl methacrylate), poly(hydroxypropyl methacrylate), poly(methacryloyloxylethyl phosphorylcholine), poly(sulfobetaine methacrylate), polyalkylene residues having more than 20 carbon atoms, DNA fragments, and poly(sulfobetaineacrylamide). A is a reactive group selected from the group consisting of active esters, amines, hydroxyl, thiol, alkoxysilane, chlorosilane, carboxylate, maleimide, vinyl sulfone, acrylamide, bromide, iodide, iodoacetate, bromoacetate, azide, aryl azide, alkyne, transcyclooctene (TCO), tetrazine, methyltetrazine, phenyltetrazine, ring-strained alkyne, bicyclononine (BCN), dibenzocyclooctin (DBCO), biotin, 2-nitrobenzyl alcohol, 5-azido-2-nitrobenzoic acid, isothiocyanate, isocyanate, benzophenone, aldehyde, dithiopyridine, methanethiosulfonate, 3-phenyl-3-(trifluoromethyl)-3H-diaziline, hydrazide, tert-butylcarbazate, phosphoramidite, epoxide, chlorotriazine, and fluorotriazine.

2. The compound according to claim 1, wherein the compound of formula I is the following compound II: 【Chemistry 2】

3. The compound according to claim 1 or 2, wherein D is O and p is 1.

4. The compound according to any one of claims 1 to 3, wherein the compound of formula I is selected from the group consisting of the following compounds IIIa: 【Transformation 3】

5. The compound according to any one of claims 1 to 4, wherein the compound of formula I is selected from the group consisting of the following compounds IV, V, and VI: 【Chemistry 4】

6. B １ and / or B ３ Is it fluoro, or B ２ and / or B ４ The compound according to any one of claims 1 to 5, wherein is hydrogen.

7. Compound of formula X: 【Transformation 5】 During the ceremony, D, L, R １ , R ２ , R ３ , and R ４ This is the same definition as the definition described in any one of claims 1 to 6, G is an A group as defined in any one of claims 1 to 6, and E １ , E ２ , E ３ , or E ４ Formed by a reaction with E １ , E ２ , E ３ , and E ４ This is selected from the following group: Here, E １ This is selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane, thermospermine, cardopentamine, cardohexamine, 1,2-diaminocyclohexane, 4,4'-diaminodiphenylsulfone, 1,5-diamino-2-methylpentane, diethylenetriamine, hexamethylenediamine, isophoronediamine, triethylenetetramine, trimethylhexamethylenediamine, spermidine, spermine, tris(2-aminoethyl)amine, tetrakis(2-aminoethyl)amine, tris(3-aminopropyl)amine, tetrakis(3-aminopropyl)ammonium, amine-terminated dendrimers, amine-functionalized silicones, polyallylamine, polyethyleneimine, polylysine, and polyornithine. E ２ This is selected from the group consisting of citric acid, succinic acid, glutamic acid, tartaric acid, malonic acid, maleic acid, poly(acrylic acid), poly(aspartic acid), poly(maleic acid-alt-ethylene), poly(nitrilotriacetic acid), poly(citric acid), and esters thereof. E ３ This is selected from the group consisting of alkoxysilanes, chlorosilanes, catechols, phosphates, phosphonates, anakelins, mimosine derivatives, gallols, thiols, N-heterocyclic carbenes, perfluorophenyl azides, benzophenones, diaryldiazomethanes, aryltrifluoromethyldiazomethanes, organoborons, α-lipoic acid, acrylamides, acrylates, and epoxides, and E ４ This is selected from the group consisting of fluorescent markers, perfluorinated alkyl groups, biotin, nitrilotriacetate (NTA), and short-chain peptides, and q is between 1 and 1000.

8. The compound according to any one of claims 1 to 7, wherein either A or G has a terminal amino group.

9. A functional polymer comprising a polymer backbone and a plurality of side chains, characterized in that at least a portion of the side chains comprises a compound according to any one of claims 1 to 8.

10. The functional polymer according to claim 9, wherein all side chains are copolymers according to any one of claims 1 to 8.

11. The functional polymer according to claim 9, wherein the functional polymer comprises at least two different side chains, and at least one of the side chains is a compound according to any one of claims 1 to 8.

12. A functional polymer according to claim 11, The functional polymer comprises further types of side chains H intended to reversibly bond to a substrate or to have a coating function, and Functional polymers in which H is selected from the following group: It may contain a heteroatom selected from the group consisting of oxygen and nitrogen, and at least one functional end group or functional side group K selected from the group consisting of amine, carboxy, poly(propylene sulfide), and thioether. １ A linear or branched chain having substituted or unsubstituted C １ ~C １２ Short-chain side chain H having an alkylene group １ ; Long-chain hydrogen containing more than 15 carbon or silicon atoms in the chain. ２ Side chain H having ２ Here, the long chain H ２ This is selected from the group consisting of polydimethylsiloxane, perfluoroether, perfluoroalkyl, polyisobutene, polyethylene glycol, polydimethylacrylamide, polyvinylpyrrolidone, polyalkyloxazoline, polyalkyloxazine, dextran, carboxymethyl dextran, poly(N-isopropylacrylamide), poly(N-hydroxyethylacrylamide), poly(2-hydroxyethyl methacrylate), poly(hydroxypropyl methacrylate), poly(methacryloyloxyethyl phosphorylcholine), poly(sulfobetaine methacrylate), polyalkylene residues having more than 20 carbon atoms, peptide chains, DNA fragments, and poly(sulfobetaineacrylamide), H ２ It does not have a functional terminal group or a functional side group; and Long chain H ３ Side chain H having ３ Here, the long chain H ３ This is selected from the group consisting of polydimethylsiloxane, perfluoroether, perfluoroalkyl, polyisobutene, polyethylene glycol, polydimethylacrylamide, polyvinylpyrrolidone, polyalkyloxazoline, polyalkyloxazine, dextran, carboxymethyl dextran, poly(N-isopropylacrylamide), poly(N-hydroxyethylacrylamide), poly(2-hydroxyethyl methacrylate), poly(hydroxypropyl methacrylate), poly(methacryloyloxyethyl phosphorylcholine), poly(sulfobetaine methacrylate), polyalkylene residues having more than 20 carbon atoms, peptide chains, DNA fragments, and poly(sulfobetaineacrylamide), H ３ This is at least one functional terminal group or functional side group K selected from the group consisting of amines, carboxylates, nitrilotriacetic acid (NTA), biotin, azides, terminal alkene groups, terminal alkyne groups, and tetrazines. ３ It holds.

13. The functional polymer comprises a further type of side chain J intended to irreversibly bond to the substrate, The side chain J may contain a heteroatom selected from the group consisting of oxygen and nitrogen, and at least one functional terminal group or functional side group K selected from the group consisting of alkoxysilane, chlorosilane, catechol, nitrocatechol, bromocatechol, chlorocatechol, phosphate, phosphonate, mimosine derivative, anaakelin, gallol, thiol, N-heterocyclic carbene, azide, perfluorophenyl azide, benzophenone, diaryldiazomethane, aryltrifluoromethyldiazomethane, organoboron, acrylamide, acrylate, and epoxide. ４ A linear or branched chain having substituted or unsubstituted C １ ~C １２ Having an alkylene group, The functional polymer according to claim 11 or 12.

14. Use of the compound according to any one of claims 1 to 8 or the polymer according to any one of claims 9 to 13 as an adhesion promoter, a thermally activated crosslinking agent, a photoactivated crosslinking agent, or a curing agent compound in a two-component adhesive.

15. Use of the compound according to any one of claims 1 to 7 for thermally introducing a functional group or fluorescent marker into a material selected from the group consisting of polymers, particles, nanoparticles, and hydrogels that essentially does not contain other functional groups.

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