CN107347909A - A kind of Si quaternary phosphine cationic antibacterial agents containing double hydroxyls and preparation method thereof - Google Patents
A kind of Si quaternary phosphine cationic antibacterial agents containing double hydroxyls and preparation method thereof Download PDFInfo
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- CN107347909A CN107347909A CN201710337683.3A CN201710337683A CN107347909A CN 107347909 A CN107347909 A CN 107347909A CN 201710337683 A CN201710337683 A CN 201710337683A CN 107347909 A CN107347909 A CN 107347909A
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- Prior art keywords
- reaction
- containing double
- cationic antibacterial
- antibacterial agents
- quaternary
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 22
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 17
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 15
- -1 phosphonium salt compounds Chemical class 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 150000002366 halogen compounds Chemical group 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000007832 Na2SO4 Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012044 organic layer Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 230000003115 biocidal effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 claims description 3
- 229940088710 antibiotic agent Drugs 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000007306 functionalization reaction Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- GTQHJCOHNAFHRE-UHFFFAOYSA-N 1,10-dibromodecane Chemical class BrCCCCCCCCCCBr GTQHJCOHNAFHRE-UHFFFAOYSA-N 0.000 claims description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical group BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 2
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical class CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000002421 anti-septic effect Effects 0.000 abstract description 14
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 description 10
- LWLSVNFEVKJDBZ-UHFFFAOYSA-N N-[4-(trifluoromethoxy)phenyl]-4-[[3-[5-(trifluoromethyl)pyridin-2-yl]oxyphenyl]methyl]piperidine-1-carboxamide Chemical compound FC(OC1=CC=C(C=C1)NC(=O)N1CCC(CC1)CC1=CC(=CC=C1)OC1=NC=C(C=C1)C(F)(F)F)(F)F LWLSVNFEVKJDBZ-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical class ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 description 1
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 1
- IXLWNFFMNULFEO-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.CO.CO.C1CCCCCCCCC1 Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.CO.CO.C1CCCCCCCCC1 IXLWNFFMNULFEO-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- KOCXMMTWVKMODE-UHFFFAOYSA-N bromobenzene;phosphane Chemical compound P.BrC1=CC=CC=C1 KOCXMMTWVKMODE-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 244000053095 fungal pathogen Species 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000007529 inorganic bases Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- MJRPMUINYAOXRW-UHFFFAOYSA-N tributylphosphane;hydrochloride Chemical compound [Cl-].CCCC[PH+](CCCC)CCCC MJRPMUINYAOXRW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/34—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-halogen bonds; Phosphonium salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/388—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Dentistry (AREA)
- Polymers & Plastics (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Materials Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
A kind of Si quaternary phosphine cationic antibacterial agents containing double hydroxyls and preparation method thereof, belong to quaternary phosphonium salt compounds technical field.The antiseptic structure is as follows：[HO‑R‑P+(Ph)2‑(CH2)x‑P+(Ph)2‑R‑O‑Q‑O‑R’‑P+(Ph)2‑(CH2)y‑P+(Ph)2‑R’‑OH]·4X‑Wherein, R and R ' is selected from C4 C10 alkoxyl phenyl, phenyl；X, y takes 4 10 integer respectively；Q is (CH2)zOr C2H4‑(O‑C2H4)m, z takes 4 10 integer, and m takes 15 integer；X is halogen compound.The present invention can be embedded in material main chain by the reaction of hydroxyl and other compounds to realize the modification to material, to be expanded the scope used of the antiseptic while solves potential spilling possibility, antibacterial timeliness length, and can not be affected by temperature during the course of the reaction.
Description
Technical field
The present invention discloses a kind of four quaternary phosphine cationic antibacterial agents containing double hydroxyls and preparation method thereof, belongs to quaternary phosphine salinization
Compound technical field.
Background technology
Antiseptic of the , quaternary alkylphosphonium salts (QPS) as a new generation, shows to pathogenic bacteria and fungi in antiseptic field
Efficient and broad spectrum of activity, or even their killing activity extends to virus and the parasite of coating, in addition, quaternary alkylphosphonium salt also has
The advantages that higher heat endurance and pH stablize (Materials Science and Engineering C 2016,61:79-
84)。
CN200810023393.2 discloses a kind of water-insoluble quaternary phosphine bactericide, using silica type inorganic material as carrier,
Surface grafting aliphatic or aromatic Dan quaternary alkylphosphonium salts functional group are made.As anti-biotic material in use, must with silica type without
Machine material is that carrier limits its use range.
CN201010546778.4 discloses a kind of phenyl-bromide Phosphonium of pi-allyl three and preparation method and application.
Document (J.Mater.Chem.B, 2015,3,1474) utilizes (3- acryloxypropyls) tributyl phosphonium chloride, three
Cyclodecane Dimethanol Diacrylate, 2- hydroxy-2-methyl -1- phenylacetones aggregate into film, and film by ultraviolet lighting
Possesses certain antibiotic property.This kind of quaternary alkylphosphonium salt is only capable of by double-bond polymerization grafting in the material because containing double bond in molecule, this
Method easily reduces the grafting rate of quaternary alkylphosphonium salt, and this external double bond easily polymerize under the high temperature conditions, therefore this kind of antiseptic can not participate in
Into the reaction of high temperature, use range is limited on the contrary.
Quaternary alkylphosphonium salt is grafted in the material by the above document or patent by the chemical bond of one end, is not related to
Can both ends embedded type quaternary alkylphosphonium salt research, and the not research on four quaternary alkylphosphonium salts.Si quaternary phosphines sun containing double hydroxyls from
Sub- antiseptic can be embedded in material main chain to realize the modification to material by the reaction of hydroxyl and other compounds, do not had not only
There is the problem of spilling, and can not be affected by temperature during the course of the reaction.In addition, Si quaternary phosphines cation is because of its increased antibacterial list
Member and unit charge amount so that the antiseptic has the anti-microbial property of enhancing.
The content of the invention
It is an object of the invention to the deficiency for above-mentioned quaternary alkylphosphonium salt, there is provided a kind of Si quaternary phosphine cations containing double hydroxyls
Antiseptic and preparation method thereof.It is low that the prepared Si quaternary phosphines cationic antibacterial agent containing double hydroxyls not only possesses general quaternary alkylphosphonium salt
The advantages of poison, low price, antibiotic property high-efficiency broad spectrum, while molecule both ends carry hydroxyl, the antiseptic can be expanded in insert material
Scope used solve simultaneously it is potential overflow possibility, in addition, Si quaternary phosphine cations enhance its antibacterial unit and unit
The quantity of electric charge, strengthen its antibiotic property.
A kind of Si quaternary phosphine cationic antibacterial agents containing double hydroxyls, it is characterised in that there is structure shown in Formulas I:
[HO-R-P+(Ph)2-(CH2)x-P+(Ph)2-R-O-Q-O-R’-P+(Ph)2-(CH2)y-P+(Ph)2-R’-OH]·
4X-
Formulas I
Wherein, R and R ' is selected from identical or different C4-C10 alkoxyl phenyl, phenyl；X, y takes 4-10 integer respectively,
It is identical or different；Q is-(CH2)z- or-C2H4-(O-C2H4)m-, z takes 4-10 integer, and m takes 1-5 integer；X is halogen family chemical combination
Thing, it preferably is selected from Cl, Br, I.
When R or R ' is selected from C4-C10 alkoxyl phenyl ,-the OH in-R-OH or-R '-OH is connected on phenyl ring or alkyl
On.
Present invention also offers a kind of preparation method with Si quaternary phosphine cationic antibacterial agent of the Formulas I containing double hydroxyls,
Comprise the following steps：
(1) one or more in structure quaternary alkylphosphonium salt shown in compound Formula II and acid binding agent are dissolved in organic reagent,
Return stirring under the conditions of 25-60 DEG C；
[HO-R-P+(Ph)2-(CH2)x-P+(Ph)2-R-OH]·2X-
Formula II
(2) the dropwise reaction thing X- (CH into above-mentioned solution2)z- X or X-C2H4-(O-C2H4)m- X (z=4-10, m=1-5,
X=Cl, Br, I), reaction continues 6~24h of return stirring, is cooled to room temperature afterwards；Gained reaction solution is concentrated after the completion of reaction
Viscous liquid is obtained, white powder target product is obtained after being washed with deicer.
The wherein synthesis of compound Formula II：By P (Ph)2-(CH2)x-P(Ph)2, p bromophenol or bromobenzene amphyl Br-
R-OH, ethylene glycol and nickelous bromide are added in reaction vessel and are passed through nitrogen, and backflow is warming up to 180 DEG C, after stirring reaction 4h
The whole, is dissolved in dichloromethane by standing system after cooling, is cleaned organic layer three times with deionized water；Afterwards
With anhydrous Na2SO4By solution dry filter, target compound Formula II is obtained after being washed with deicer to organic phase.
Acid binding agent is inorganic base potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, or organic bases triethylamine, pyridine,
It is preferred that potassium carbonate, potassium hydroxide.
Organic solvent is DMF, preferably dichloromethane, DMF.
Reactants of X-(CH2)z- X (z=4-10, X=Cl, Br, I), preferential 1,6- dibromo-hexanes, 1,6- dichloro hexanes, 1,
10- dibromo-decanes, the chlorodecanes of 1,10- bis-.
Reactants of X-C2H4-(O-C2H4)m- X (m=1-5, X=Cl, Br, I), preferably Br-C2H4-O-C2H4-Br、Br-
C2H4-O-C2H4-O-C2H4-Br。
Deicer is tetrahydrofuran, ether, preferential tetrahydrofuran.
A kind of described Si quaternary phosphine cationic antibacterial agents containing double hydroxyls can be applied to medicine equipment, coating, yarn fabric
In the field such as household electrical appliances, required functionalization anti-biotic material is prepared.Further preferably, in insert material.
Compared with existing antiseptic, advantage is prepared antiseptic：
(1) possesses the advantages of quaternary alkylphosphonium salt antiseptic low toxicity, low price, antibiotic property high-efficiency broad spectrum.
(2) designing two sections of quaternary alkylphosphonium salts has double hydroxyls, can be in insert material, and the scope used for expanding the antiseptic is same
When solve it is potential overflow possibility, antibacterial timeliness length, while can not be affected by temperature during the course of the reaction.
(3) quaternary alkylphosphonium salt antibacterial unit and unit charge amount are enhanced, strengthens its antibiotic property.
Brief description of the drawings
Fig. 1 is the hydrogen spectrum of compound B-11 in embodiment 1.
Fig. 2 is the hydrogen spectrum of the target product finally synthesized in embodiment 1.
Fig. 3 is that the Si quaternary phosphines cationic antibacterial agent containing double hydroxyls in embodiment 8 is embedded in main chain schematic diagram.
Fig. 4 is that antibacterial of the film in different time to Escherichia coli and staphylococcus aureus is prepared in embodiment 8
Result figure.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.
Embodiment 1
Compound B-11 is synthesized first：Take double (diphenylphosphine) hexanes (1.14g, 2.5mmol) of 1,6-, p bromophenol
(2.16g, 12.5mmol), ethylene glycol 5mL and nickelous bromide 50mg are added in 50mL there-necked flask and are passed through nitrogen, and backflow rises
Temperature is to 180 DEG C.System is stood after magnetic agitation reaction 4h, the whole is dissolved in 20mL dichloromethane after cooling,
Organic layer is cleaned three times with deionized water.Afterwards with anhydrous Na2SO4By solution dry filter, respectively with a large amount of ether and a large amount of
Tetrahydrofuran washs to organic phase, obtains compound B-11 afterwards.
Compound A1 (0.4g, 1.64mmol) is taken, and compound B-11 (2.3g, 3.61mmol), potassium carbonate (1.0g,
7.24mmol), DMF 20mL are added in 100mL single-necked flask, the magnetic agitation backflow 8h under the conditions of 50 DEG C.Question response knot
Room temperature is cooled to after beam.Then the whole is dissolved in 20mL dichloromethane.Organic layer is cleaned three with deionized water
Time, afterwards with anhydrous Na2SO4By solution dry filter, organic phase is washed with a large amount of tetrahydrofurans, obtains white powder
Shape target product.
Embodiment 2
Compound A2 (0.5g, 1.64mmol) is taken, and compound B-11 (2.3g, 3.61mmol), sodium carbonate (0.7g,
7.24mmol), DMF 20mL are added in 100mL single-necked flask, the magnetic agitation backflow 8h under the conditions of 50 DEG C.Question response knot
Room temperature is cooled to after beam.Then the whole is dissolved in 20mL dichloromethane.Organic layer is cleaned three with deionized water
Time, afterwards with anhydrous Na2SO4By solution dry filter, organic phase is washed with a large amount of tetrahydrofurans, obtains white powder
Shape target compound.
Embodiment 3
Compound A-13 (0.35g, 1.64mmol) is taken, and compound B-11 (2.3g, 3.61mmol), potassium carbonate (1.0g,
7.24mmol), dichloromethane 20mL is added in 100mL single-necked flask, the magnetic agitation 24h under the conditions of 25 DEG C.Question response
Room temperature is cooled to after end.Then the whole is dissolved in 20mL dichloromethane.Organic layer is cleaned with deionized water
Three times, afterwards with anhydrous Na2SO4By solution dry filter, organic phase is washed with a large amount of tetrahydrofurans, obtains white powder
Last shape target product.
Embodiment 4
Compound A4 (0.38g, 1.64mmol) is taken, and compound B-11 (2.3g, 3.61mmol), potassium hydroxide (0.4g,
7.24mmol), dichloromethane 20mL is added in 100mL single-necked flask, the magnetic agitation 24h under the conditions of 25 DEG C.Question response
Room temperature is cooled to after end.Then the whole is dissolved in 20mL dichloromethane.Organic layer is cleaned with deionized water
Three times, afterwards with anhydrous Na2SO4By solution dry filter, organic phase is washed with a large amount of tetrahydrofurans, obtains white powder
Last shape target product.
Embodiment 5
Compound A-45 (0.45g, 1.64mmol) is taken, and compound B-11 (2.3g, 3.61mmol), potassium hydroxide (0.4g,
7.24mmol), dichloromethane 20mL is added in 100mL single-necked flask, the magnetic agitation 24h under the conditions of 25 DEG C.Question response
Room temperature is cooled to after end.Then the whole is dissolved in 20mL dichloromethane.Organic layer is cleaned with deionized water
Three times, afterwards with anhydrous Na2SO4By solution dry filter, organic phase is washed with a large amount of ether, obtains white powder
Target product.
Embodiment 6
Compound B2 is synthesized first：Take double (diphenylphosphine) hexanes (2.28g, 5mmol) of 1,6-, 6- (4- bromobenzenes epoxide) oneself
Alcohol (5.0g, 20mmol), ethylene glycol 10mL and nickelous bromide 50mg are added in 50mL there-necked flask and are passed through nitrogen, and backflow rises
Temperature is to 180 DEG C.System is stood after magnetic agitation reaction 4h, the whole is dissolved in 20mL dichloromethane after cooling,
Organic layer is cleaned three times with deionized water.Afterwards with anhydrous Na2SO4By solution dry filter, respectively with a large amount of ether and a large amount of
Tetrahydrofuran washs to organic phase, obtains compound B2 afterwards.
Compound A1 (0.4g, 1.64mmol) is taken, and compound B2 (3.6g, 3.61mmol), potassium carbonate (1.0g,
7.24mmol), DMF 20mL are added in 100mL single-necked flask, the magnetic agitation backflow 8h under the conditions of 50 DEG C.Question response knot
Room temperature is cooled to after beam.Then the whole is dissolved in 20mL dichloromethane.Organic layer is cleaned three with deionized water
Time, afterwards with anhydrous Na2SO4By solution dry filter, organic phase is washed with a large amount of ether, obtains white powder mesh
Mark product.
Embodiment 7
Compound B3 is synthesized first：Take double (diphenylphosphine) hexanes (1.37g, 3mmol) of 1,6-, 10- (4- bromobenzenes epoxide)
Decyl alcohol (3.9g, 12mmol), ethylene glycol 10mL and nickelous bromide 50mg are added in 50mL there-necked flask and are passed through nitrogen, backflow
It is warming up to 180 DEG C.System is stood after magnetic agitation reaction 4h, the whole is dissolved in 20mL dichloromethane after cooling
In, organic layer is cleaned three times with deionized water.Afterwards with anhydrous Na2SO4By solution dry filter, respectively with a large amount of ether and
A large amount of tetrahydrofurans wash to organic phase, obtain compound B3 afterwards.
Compound A1 (0.4g, 1.64mmol) is taken, and compound B3 (4.0g, 3.61mmol), potassium hydroxide (0.4g,
7.24mmol), dichloromethane 20mL is added in 100mL single-necked flask, the magnetic agitation 24h under the conditions of 25 DEG C.Question response
Room temperature is cooled to after end.Then the whole is dissolved in 20mL dichloromethane.Organic layer is cleaned with deionized water
Three times, afterwards with anhydrous Na2SO4By solution dry filter, organic phase is washed with a large amount of ether, obtains white powder
Target product.
Embodiment 8
The double hydroxyl Si quaternary alkylphosphonium salts (1wt%) that will be obtained in embodiment 1, IPDI IPDI (1.04g)
It is added to 100mL and carries mechanical agitator, in the three-necked flask of thermometer, is warming up to 45 DEG C under mechanical stirring.Then to bottle
The middle dibutyl tin laurate for adding catalytic amount, PPG is slowly added dropwise after one minute with constant pressure funnel again
HSH330N (8.63g), is warming up to 60 DEG C, keeping temperature reacts 1-2h again after being added dropwise by system.The system for the treatment of is cooled to 45 DEG C
Afterwards, hydroxy-ethyl acrylate 0.2g is added dropwise to system with constant pressure funnel to block system.Isocyanic acid in detection architecture
Ester group, when detection isocyanate groups have reacted, reaction terminates, that is, has obtained oligomer.
By the oligomer of preparation, reactive diluent and light trigger D1173 with mass percent=5/4.7/0.3 (wt%)
Add in beaker and stir.Then it is uniformly applied on one piece of 50mm × 50mm polycarbonate plate, then covers one layer
Polyethylene film, the generation of oxygen inhibition during avoiding illumination.In high-pressure sodium lamp (light intensity=40mWcm-2) under expose certain time
Obtain the functionalization photocuring film that double quaternary alkylphosphonium salt antiseptics of hydroxyl four are modified to obtain.
Claims (10)
1. a kind of Si quaternary phosphine cationic antibacterial agents containing double hydroxyls, it is characterised in that there is structure shown in Formulas I:
[HO-R-P+(Ph)2-(CH2)x-P+(Ph)2-R-O-Q-O-R’-P+(Ph)2-(CH2)y-P+(Ph)2-R’-OH]·4X-
Formulas I
Wherein, R and R ' is selected from identical or different C4-C10 alkoxyl phenyl, phenyl；X, y takes 4-10 integer respectively, identical
It is or different；Q is-(CH2)z- or-C2H4-(O-C2H4)m-, z takes 4-10 integer, and m takes 1-5 integer；X is halogen compound,
Selected from Cl, Br, I.
A kind of 2. Si quaternary phosphine cationic antibacterial agents containing double hydroxyls according to claim 1, it is characterised in that as R or
When R ' is selected from C4-C10 alkoxyl phenyl ,-the OH in-R-OH or-R '-OH is connected on alkyl or on phenyl ring.
3. preparing a kind of method of Si quaternary phosphine cationic antibacterial agents containing double hydroxyls described in claim 1 or 2, its feature exists
In comprising the following steps：
(1) the double quaternary alkylphosphonium salts of structure shown in compound Formula II and acid binding agent are dissolved in organic reagent, flowed back under the conditions of 25-60 DEG C
Stirring；
[HO-R-P+(Ph)2-(CH2)x-P+(Ph)2-R-OH]·2X-
Formula II
(2) the dropwise reaction thing X- (CH into above-mentioned solution2)z- X or X-C2H4-(O-C2H4)m- X, z=4-10, m=1-5, X=
Cl, Br, I, reaction continue 6~24h of return stirring, are cooled to room temperature afterwards；Gained reaction solution is concentrated to give after the completion of reaction viscous
Thick liquid, white powder target product is obtained after being washed with deicer.
4. according to the method for claim 3, it is characterised in that the wherein synthesis of compound Formula II：By P (Ph)2-(CH2)x-P
(Ph)2, p bromophenol or bromobenzene amphyl Br-R-OH, ethylene glycol and nickelous bromide be added in reaction vessel and be passed through nitrogen
Gas, backflow are warming up to 180 DEG C, system are stood after stirring reaction 4h, the whole is dissolved in dichloromethane after cooling,
Organic layer is cleaned three times with deionized water；Afterwards with anhydrous Na2SO4By solution dry filter, organic phase is carried out with deicer
Target compound Formula II is obtained after washing.
5. according to the method for claim 3, it is characterised in that acid binding agent be selected from inorganic base potassium carbonate, sodium carbonate, potassium hydroxide,
Sodium hydroxide, or organic bases triethylamine, pyridine.
6. according to the method for claim 3, it is characterised in that organic solvent is selected from DMF, dichloromethane.
7. according to the method for claim 3, it is characterised in that reactants of X-(CH2)z- X is selected from 1,6- dibromo-hexanes, 1,6- dichloros
Hexane, 1,10- dibromo-decanes, the chlorodecanes of 1,10- bis-；Reactants of X-C2H4-(O-C2H4)m- X is selected from Br-C2H4-O-C2H4-Br、
Br-C2H4-O-C2H4-O-C2H4-Br。
8. according to the method for claim 3, it is characterised in that deicer is tetrahydrofuran, ether, preferential tetrahydrofuran.
9. the application of the Si quaternary phosphine cationic antibacterial agents containing double hydroxyls described in claim 1 or 2, applied to medicine equipment,
Coating, yarn fabric and household electrical appliances.
10. according to the application of claim 9, the four quaternary phosphine cationic antibacterial agent insert materials containing double hydroxyls are prepared into functionalization
Anti-biotic material.
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