CN117417234A - Preparation method of fluoroalkyl ether telechelic compound and intermediate thereof - Google Patents
Preparation method of fluoroalkyl ether telechelic compound and intermediate thereof Download PDFInfo
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- CN117417234A CN117417234A CN202311384281.0A CN202311384281A CN117417234A CN 117417234 A CN117417234 A CN 117417234A CN 202311384281 A CN202311384281 A CN 202311384281A CN 117417234 A CN117417234 A CN 117417234A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 58
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- -1 fluoroalkyl ether Chemical compound 0.000 title claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000006192 iodination reaction Methods 0.000 claims abstract description 29
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims abstract description 18
- 238000011282 treatment Methods 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims description 47
- 239000003638 chemical reducing agent Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 238000006722 reduction reaction Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 150000002825 nitriles Chemical class 0.000 claims description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- 150000001408 amides Chemical class 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 159000000000 sodium salts Chemical group 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004210 ether based solvent Substances 0.000 claims description 6
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 6
- 235000019252 potassium sulphite Nutrition 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 150000003462 sulfoxides Chemical class 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005456 alcohol based solvent Substances 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 2
- 229940125904 compound 1 Drugs 0.000 claims description 2
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 239000000543 intermediate Substances 0.000 abstract description 4
- 238000010667 large scale reaction Methods 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 17
- 239000011737 fluorine Substances 0.000 description 17
- 125000001424 substituent group Chemical group 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920001774 Perfluoroether Polymers 0.000 description 3
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 150000001265 acyl fluorides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
- C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/04—Sulfinic acids; Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/12—Saturated ethers containing halogen
- C07C43/123—Saturated ethers containing halogen both carbon chains are substituted by halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of fluoroalkyl ether telechelic compounds and intermediates thereof. The preparation method of the fluoroalkyl ether telechelic compound comprises the following steps: in a solvent, optionally in the presence of an oxidizing agent, a compound of formula II and I 2 And (3) carrying out iodination reaction shown below to obtain the compound of the formula I. The preparation method of the invention has at least the advantages of high conversion yield, simple post-treatment and suitability for one or more of large-scale reactions.
Description
Technical Field
The invention relates to a preparation method and an intermediate of a fluoroalkyl ether telechelic compound.
Background
The fluorine-containing telechelic compound is an important organic fluorine-containing intermediate, is an important raw material for producing fluorine-containing polyurethane, fluorine-containing surfactant, fluorine-containing ether adhesive, fluorine-containing fabric finishing agent and other fluorine-containing fine chemicals, has the characteristics of high surface activity, high weather resistance, high chemical stability, hydrophobicity and oleophobicity and the like, and has wide application in the industries of chemical industry, materials, electronics, military industry, aerospace and the like.
The classical approach for the preparation of fluoroether telechelic compounds is to telomerize by acyl fluoride and HFPO followed by functionalization (US 3322826) and then to telomerize various fluoroolefins and oxygen under light (EP 0089820A1; US3442942; US4451646; J. Fluoro. Chem.1986,33,314). The method has the advantages of harsh reaction conditions, high requirements on equipment, certain dangers and non-singleness of reaction products, and can obtain the target product after the separation and purification are subjected to complex post-treatment such as acid-base neutralization, non-toxic and harmless post-treatment and fine and complex rectification.
Functionalization can also be carried out by means of specific substrates (J.Polym. Sci.1972,10,947.). The method has the disadvantages of difficult obtainment of raw materials, low conversion yield and inapplicability to mass preparation.
Disclosure of Invention
The technical problem to be solved by the invention is at least to overcome the defect of low conversion yield of the preparation method of the fluoroalkyl ether telechelic compound in the prior art, thereby providing the preparation method of the fluoroalkyl ether telechelic compound. The preparation method of the invention has at least the advantages of high conversion yield, simple post-treatment and suitability for one or more of large-scale reactions.
The invention mainly solves the technical problems through the following technical scheme.
The invention provides a preparation method of a compound shown in a formula I, which comprises the following steps: in a solvent, optionally in the presence of an oxidizing agent, a compound of formula II and I 2 Carrying out iodination reaction as shown below to obtain the compound of the formula I; wherein the solvent is selected from organic solvents or mixed solvents of organic solvents and water, and the organic solvents are selected from one or more of nitrile solvents, ether solvents, amide solvents, alcohol solvents and sulfoxide solvents; the oxidant is Na 2 S 2 O 8 、K 2 S 2 O 8 Cerium ammonium nitrate or (NH) 4 ) 2 S 2 O 8 ；
Wherein M is Na or K, n is 0 or 1, wherein R 1 、R 2 、R 3 And R is 4 Each independently is H, halogen, C 1-6 Alkyl, C substituted by one or more halogens 1-6 An alkyl group.
In the iodination reaction, the molar volume ratio of the compound of formula II and the solvent is a molar volume ratio conventional in such reactions in the art, for example, 0.1 to 10mol/L, preferably 0.2 to 2mol/L, more preferably 1 to 2mol/L or 0.2 to 0.3mol/L, for example, 1.16mol/L or 0.24mol/L.
In one embodiment, the volume ratio of the organic solvent to water in the iodination reaction is 1:3 to 3:1, preferably 1:2 to 2:1, for example 1:1.
In one embodiment, in the iodination reaction, the nitrile solvent is preferably acetonitrile in the organic solvent. The ether solvent is preferably selected from one or more of tetrahydrofuran, dioxane and tetraethylene glycol dimethyl ether. The amide solvent is preferably one or two selected from N, N-dimethylformamide and N, N-dimethylacetamide. The alcohol solvent is preferably diethylene glycol. The sulfoxide solvent is preferably dimethyl sulfoxide.
In one embodiment, the organic solvent is preferably selected from one or more of an ether solvent, an alcohol solvent and a sulfoxide solvent, more preferably selected from one or more of tetrahydrofuran, diethylene glycol and dimethyl sulfoxide.
In one embodiment, in the iodination reaction, the I 2 And the molar ratio of the compounds of the formula II is from 1:1 to 5:1, preferably from 2:1 to 3:1, for example 2.02:1 or 2.59:1.
In one embodiment, the molar ratio of the oxidizing agent to the compound of formula II in the iodination reaction is 1:1 to 2:1, for example 1.89:1 or 1.08:1.
In one embodiment, R 1 、R 2 、R 3 And R is 4 In the above, the C 1-6 Alkyl groups are each independently preferably C 1-3 Alkyl groups, more preferably methyl groups. The halogens are each independently preferably F, cl or Br.
In one embodiment, R 1 、R 2 、R 3 And R is 4 Each independently H, C 1-6 Alkyl or C substituted by one or more halogens 1-6 Alkyl, preferably H or C 1-6 Alkyl, more preferably H.
The reaction temperature of the iodination reaction is a reaction temperature conventional in such reactions in the art, for example, the reaction is carried out at room temperature and does not exceed 80 to 90 ℃. The room temperature generally means 20-30 ℃. The reaction temperature is preferably room temperature.
The progress of the iodination reaction may be measured using methods commonly used in the art (e.g 19 F-NMR) is generally used as end point for the reaction when the starting compounds disappear or no longer react or the product no longer increases. For example, the reaction time of the reaction is 2h.
The gases generated during the iodination reaction are absorbed by an alkaline solution, such as sodium hydroxide, which is conventionally used in such reactions in the art.
In one embodiment, the process for the preparation of the compound of formula I may further comprise the following post-treatment steps: and after the iodination reaction is finished, adding a reducing agent until the color of the reaction liquid is removed, and adding water and then separating the liquid to obtain the compound of the formula I.
The reducing agent used in the post-treatment may be a reducing agent conventionally used in such post-treatments in the art, for example sodium thiosulfate or sodium bisulphite. The reducing agent may be configured as a saturated aqueous solution for use in the aftertreatment.
In one embodiment, M is preferably Na when n is 0 in the iodination reaction. The molar volume ratio of the compound of formula II to the solvent is preferably 1 to 2mol/L, for example 1.16mol/L. The organic solvent is preferably an ether solvent, more preferably tetrahydrofuran.
In one embodiment, M is preferably K when n is 1 in the iodination reaction. The molar volume ratio of the compound of formula II to the solvent is preferably from 0.2 to 0.3mol/L, for example 0.24mol/L. The organic solvent is preferably an alcohol solvent, more preferably diethylene glycol.
In one embodiment, the process for preparing a compound of formula I further comprises a process for preparing a compound of formula II comprising the steps of: in a solvent, carrying out reduction reaction on a compound of the formula III in the presence of a reducing agent to obtain a compound of the formula II; wherein the solvent is selected from organic solvents and water, and the organic solvents are selected from one or more of nitrile solvents, ether solvents and amide solvents;
wherein n is 0 or 1, R 1 、R 2 、R 3 And R is 4 Is defined as in any one of the present inventions;
when n is 0, the reducing agent is a sodium salt reducing agent, and M is Na; when n is 1, the reducing agent is a sodium salt reducing agent or a potassium salt reducing agent, and M is corresponding Na or K.
In the reduction reaction, the solvent is used in an amount conventional in such a reaction in the art, for example, the molar volume ratio of the compound of formula III to the solvent is 0.2 to 1mol/L, preferably 0.4 to 0.7mol/L.
In one embodiment, the volume ratio of the organic solvent to water in the reduction reaction is 1:10 to 10:1, preferably 1:3 to 3:1, more preferably 1:2 to 2:1, for example 1:1 or 2:3.
In one embodiment, in the reduction reaction, the nitrile solvent is preferably acetonitrile in the organic solvent. The ether solvent is preferably selected from one or two of tetrahydrofuran and dioxane. The amide solvent is preferably N, N-dimethylformamide.
In one embodiment, the organic solvent is preferably one or two selected from an ether solvent and a nitrile solvent, more preferably one or more selected from tetrahydrofuran, dioxane and acetonitrile, and further preferably one or two selected from tetrahydrofuran and dioxane.
In one embodiment, the molar ratio of the reducing agent to the compound of formula III is from 2:1 to 8:1, preferably from 2:1 to 5:1, for example 2.5:1 or 3.5:1.
In one embodiment, the sodium salt reducing agent is preferably selected from one or both of sodium sulfite and sodium tetrahydroborate, more preferably sodium sulfite. The potassium salt reducing agent is preferably one or both selected from potassium sulfite and potassium tetrahydroborate, more preferably potassium sulfite.
In one embodiment, in the reduction reaction, when n is 1, the reducing agent is preferably the potassium salt reducing agent, and M is K.
In one embodiment, in the reduction reaction, when M is K, the reducing agent is preferably potassium sulfite. The organic solvent is preferably tetrahydrofuran. The volume ratio of the organic solvent to water is preferably 1:1. The molar ratio of the reducing agent to the compound of formula III is preferably 3.5:1.
In one embodiment, in the reduction reaction, when M is Na, the reducing agent is preferably sodium sulfite. The organic solvent is preferably dioxane. The volume ratio of the organic solvent to water is preferably 2:3. The molar ratio of the reducing agent to the compound of formula III is preferably 2.5:1.
The reaction temperature of the reduction reaction is a reaction temperature conventional in the art for such reactions, for example, the reaction temperature is-30 to 160 ℃; preferably 0-80 c, more preferably 20-30 c. The reaction is preferably carried out at room temperature. The room temperature generally means 20-30 ℃.
The progress of the reduction reaction may be measured by methods commonly used in the art (e.g 19 F-NMR) is generally used as end point for the reaction when the starting compounds disappear or no longer react or the product no longer increases. For example, the followingThe reaction time of the reduction reaction was 10 hours.
SO generated during the reduction reaction 2 The isogas is absorbed by an alkali lye, such as sodium hydroxide alkali lye, which is conventionally used in such reactions in the art.
In one embodiment, the process for the preparation of the compound of formula II further comprises the following post-treatment steps: and after the reduction reaction is finished, removing the solvent, adding the organic solvent, stirring, filtering, and concentrating the obtained filtrate. The organic solvent is preferably an ester solvent, more preferably ethyl acetate.
The invention also provides a compound which is a compound of formula I or a compound of formula II shown below;
wherein n is 1, M, R 1 、R 2 、R 3 And R is 4 Is defined as in any one of the present inventions.
The present invention also provides a compound selected from the group consisting of compound 1, compound 2, and compound 2' shown below:
the invention also provides a preparation method of the compound of the formula II, wherein the conditions and the operation of the preparation method of the compound of the formula II are as described in any one of the invention.
The invention also provides application of the compound of the formula II in preparing the compound of the formula I.
The invention also provides application of the compound 2 or the compound 2' in preparing the compound of the formula I.
In addition to the foregoing, when used in the specification and claims of this application, the following terms have the meanings indicated below, unless specifically indicated otherwise.
Certain chemical groups defined herein are preceded by a simplified symbol to indicate the total number of carbon atoms present in the group. For example, C 1-6 Alkyl refers to an alkyl group having a total of 1, 2, 3, 4, 5, or 6 carbon atoms. The total number of carbon atoms in the reduced notation does not include carbon that may be present in a substituent of the group.
In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a specific substituent. Further, when the group is substituted with 1 or more of the substituents, the substituents are independent of each other, that is, the 1 or more substituents may be different from each other or the same. Unless otherwise indicated, a substituent group may be substituted at each substitutable position of the substituted group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, then the substituents may be the same or different at each position.
In the various parts of the present specification, substituents of the presently disclosed compounds are disclosed in terms of the type or scope of groups. It is specifically noted that the present invention includes each individual subcombination of the individual members of these group classes and ranges. The term "C x-y Alkyl "refers to a straight or branched chain saturated hydrocarbon containing from x to y carbon atoms. For example, the term "C 1 -C 6 Alkyl "or" C 1-6 Alkyl "means in particular methyl, ethyl, C independently disclosed 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 An alkyl group; "C 1-3 Alkyl "refers specifically to independently disclosed methyl, ethyl, C 3 Alkyl (i.e., propyl, including n-propyl and isopropyl).
When none of the recited substituents indicates through which atom it is attached to a chemical structural formula (including but not specifically mentioned compounds), such substituents may be bonded through any atom thereof. Combinations of substituents and/or variants thereof are permissible only if such combinations result in stable compounds.
When any variable (e.g. R 1-a ) In the definition of a compound, the definition of each position of the variable is independent of the definition of the other positions, and the meanings of the variable are independent and do not influence each other. Thus, if a group is substituted with 1, 2 or 3R 1-a The radical is substituted, that is to say, it may be substituted by up to 3R 1-a Substituted, where a position R 1-a Definition of (d) and the remaining position R 1-a Are defined independently of each other. In addition, combinations of substituents and/or variables are allowed only if the combination yields a stable compound.
Where no substituent is explicitly indicated in a recited group, such a group is merely unsubstituted. For example when "C 1-4 Alkyl "not previously" substituted or unsubstituted "refers only to" C 1-4 Alkyl "as such or" unsubstituted C 1-4 An alkyl group.
The term "halogen" refers to fluorine, chlorine, bromine or iodine, in particular F, cl or Br.
The above-mentioned preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, so as to obtain the preferred embodiments of the present invention.
The reagents and starting materials used in the present invention are commercially available.
The Chinese corresponding to English or English abbreviations in the present invention is as follows, unless otherwise specified:
the invention has the positive progress effects that: the preparation method can accurately synthesize a series of fluoroalkyl ether telechelic compounds, and the raw materials are cheap and easy to obtain. Compared with the existing synthesis method of fluoroether telechelic compounds, the method has one or more of the following advantages: the synthesis is accurate, the method is simple and convenient, the yield is high, the post-treatment is simple, the yield can be maintained even in large-scale reaction, the method is greatly superior to the existing synthesis method of fluoroether telechelic compounds, and the method has wide application prospect in the field of fluorine-containing materials.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The structure and purity of the compound are improved by nuclear magnetic resonance 19 F NMR) technique, and using a Bruker AVANCE 300 type NMR, the solvent was determined as the solvent used for the reaction.
EXAMPLE 1 ICF 2 CF 2 OCF 2 CF 2 Preparation of I (formula I-1)
(1)
Into a 10L flask equipped with mechanical stirring was added the mixed solvent Dioxane: h 2 O=2:3 (7L), the starting material (2 kg,4.7 mol) represented by formula (III) was weighed into a reaction flask, and the reaction system was layered. Weighing reducing agent Na 2 SO 3 (1492 g,11.7 mol) and reacted for 10 hours under the condition of maintaining the rotating speed of 300 revolutions per minute at room temperature and fully stirring, and the reaction emits gas SO 2 The gas is absorbed using lye sodium hydroxide. After the completion of the fluorine spectrum detection reaction, the reaction solvent was distilled off, then EA (4L) was added and stirred for 1 hour, the resulting white suspension was filtered, and the filtrate was collected and concentrated on a diaphragm pump to obtain a sodium sulfinate salt represented by the formula (II-1) as a white foamy solid (2 kg, yield 99%).
19 F NMR(376MHz,Acetone)δppm-68.89(q,2F),-83.25(q,2F),-86.25(m,2F),-133.76(d,2F).
(2)
Into a 10L glass kettle containing sodium sulfinate represented by the formula (II-1) (2 kg,4.653 mol), then adding solvent THF: H 2 O=1:1 (4L), after mechanical stirring (300 rpm) to dissolve the sulfinate, oxidant K was added in 3 portions 2 S 2 O 8 (1364 g,5.04 mol) and I 2 Together (2387.6 g,9.4 mol) the reaction is bubble-free, the gas is absorbed by sodium hydroxide lye and exothermic, the temperature is kept not to exceed 80 ℃. After the addition was completed, the reaction was carried out at room temperature for 2 hours. After the completion of the fluorine spectrum detection reaction, a saturated sodium hydrogensulfite solution (5L) was added until the color of the reaction solution was removed. And continuously adding a large amount of water to enable the product shown as the formula (I-1) to become an independent fluorine phase and be enriched at the bottom of the reaction liquid. After separation, 1787g of pale yellow oily product is obtained in total, 78% of total yield and 95% of purity in two steps.
19 F NMR(376MHz,Chloroform-d)δppm-65.01(s,4F),-86.38(s,4F).
Example 2 ICH 2 CH 2 CF 2 CF 2 OCF 2 CF 2 Preparation of I (1-5)
(1)
Into a 3L flask equipped with mechanical stirring was added the mixed solvent THF: h 2 O=1:1 (2L), the starting material (454 g,1 mol) represented by formula (IV) was weighed into a reaction flask, and the reaction system was layered. Weighing reducing agent K 2 SO 3 (554 g,3.5 mol) was reacted at room temperature under stirring at 300 rpm for 16h with evolution of gaseous SO 2 The gas is absorbed using lye sodium hydroxide. After the completion of the fluorine spectrum detection reaction, the reaction solvent was distilled off, then EA (4L) was added and stirred for 1 hour, and the resulting white suspension was filtered, and the filtrate was collected and concentrated on a diaphragm pump to obtain a potassium sulfinate salt represented by the formula (II-2) as a white foamy solid (458 g, yield 99%).
19 F NMR(376MHz,EA)δppm-78.8(m,2F),-83.7(m,2F),-114.5(m,2F),-129.4(m,2F)。
(2)
Into a 3L glass kettle containing a potassium sulfinate salt (458 g,0.9665 mol) represented by the formula (II-2), a solvent Dg: H was then added 2 O=1:1 (4L), after mechanical stirring (300 rpm) to dissolve the sulfinate, oxidant Na was added 2 S 2 O 4 (433 g,1.83 mol) was added in 3 portions 2 Together (635 g,2.5 mol) the reaction is bubble-free, gas is absorbed by sodium hydroxide lye and exothermic, taking care that the temperature is not kept above 90 ℃. After the addition was completed, the reaction was carried out at room temperature for 2 hours. After the fluorine spectrum detection reaction was completed, a saturated sodium hydrogensulfite solution (4L) was added until the color of the reaction solution was removed. And continuously adding a large amount of water to enable the product shown as the formula (I-5) to become an independent fluorine phase and be enriched at the bottom of the reaction liquid. After separation, 383.6g of a pale yellow oily product is obtained in total, the total yield of the two steps is 77%, and the purity is 95%.
19 F NMR(376MHz,Chloroform-d)δppm-65.01(m,2F),-86.1(m,2F),-88.1(m,2F),-118.7(m,2F)。
Example 3
Note that: a II(10mmol,1.0equiv.)，I 2 (20 mmol,2.0 equiv.) solvent (20 mL, 0.5M), 50mL eggplant-shaped bottle, magnetic stirring for 5h. b And detecting by using benzotrifluoride as an internal standard fluorine spectrum. c Adding K 2 S 2 O 8 (10 mmol,1.0 equiv.) after substrate conversion was complete. d 40mmol scale, isolated in yield. The remainder of the procedure is as in example 1 (1). The solvent used in this example was an organic solvent, and it was found that the subsequent addition of water to the solvent did not affect the reaction, and was capable ofCan reduce the use of organic solvents, reduce the reaction cost and is more beneficial to industrial production.
Example 4
Note that: a III-1 (10 mmol,1.0 equiv.), solvent (30 mmol,3.0 equiv.), solvent (30 mL, 0.33M), 50mL eggplant-shaped bottle, magnetic stirring for 12h, monitoring in real time to adjust the reaction temperature time. b And detecting by using benzotrifluoride as an internal standard fluorine spectrum. c 40mmol scale. The remainder of the procedure is as in example 1 (2).
Claims (10)
1. A process for the preparation of a compound of formula I, comprising the steps of: in a solvent, optionally in the presence of an oxidizing agent, a compound of formula II and I 2 Carrying out iodination reaction as shown below to obtain the compound of the formula I; wherein the solvent is selected from organic solvents or mixed solvents of organic solvents and water, and the organic solvents are selected from one or more of nitrile solvents, ether solvents, amide solvents, alcohol solvents and sulfoxide solvents; the oxidant is Na 2 S 2 O 8 、K 2 S 2 O 8 Cerium ammonium nitrate or (NH) 4 ) 2 S 2 O 8 ；
Wherein M is Na or K, n is 0 or 1, wherein R 1 、R 2 、R 3 And R is 4 Each independently is H, halogen, C 1-6 Alkyl, C substituted by one or more halogens 1-6 An alkyl group.
2. The preparation method according to claim 1, characterized in that it satisfies one or more of the following conditions:
(1) In the iodination reaction, the molar volume ratio of the compound of formula II to the solvent is 0.1 to 10mol/L, preferably 0.2 to 2mol/L, more preferably 1 to 2mol/L or 0.2 to 0.3mol/L, for example 1.16mol/L or 0.24mol/L;
(2) In the iodination reaction, the volume ratio of the organic solvent to the water is 1:3-3:1, preferably 1:2-2:1, for example 1:1;
(3) In the iodination reaction, acetonitrile is used as the nitrile solvent in the organic solvent;
(4) In the iodination reaction, the ether solvent is selected from one or more of tetrahydrofuran, dioxane and tetraethylene glycol dimethyl ether;
(5) In the iodination reaction, in the organic solvent, the amide solvent is selected from one or two of N, N-dimethylformamide and N, N-dimethylacetamide;
(6) In the iodination reaction, the alcohol solvent is diethylene glycol in the organic solvent;
(7) In the iodination reaction, the sulfoxide solvent is dimethyl sulfoxide in the organic solvent;
(8) In the iodination reaction, the I 2 And the molar ratio of the compounds of the formula II is from 1:1 to 5:1, preferably from 2:1 to 3:1, for example 2.02:1 or 2.59:1;
(9) In the iodination reaction, the molar ratio of the oxidant to the compound of formula II is 1:1 to 2:1, for example 1.89:1 or 1.08:1;
(10)R 1 、R 2 、R 3 and R is 4 In the above, the C 1-6 Alkyl groups are each independently C 1-3 Alkyl, preferably methyl;
(11)R 1 、R 2 、R 3 and R is 4 Wherein each halogen is independently F, cl or Br.
3. The preparation method according to claim 1 or 2, characterized in that it satisfies one or more of the following conditions:
(1) In the iodination reaction, the organic solvent is selected from one or more of ether solvents, alcohol solvents and sulfoxide solvents, preferably one or more of tetrahydrofuran, diethylene glycol and dimethyl sulfoxide;
(2)R 1 、R 2 、R 3 and R is 4 Each independently H, C 1-6 Alkyl or C substituted by one or more halogens 1-6 Alkyl, preferably H or C 1-6 Alkyl, more preferably H;
(3) The iodination reaction is carried out at room temperature, and the reaction temperature of the iodination reaction is not more than 80-90 ℃;
(4) The gas generated in the iodination reaction process is absorbed by alkali liquor, such as sodium hydroxide alkali liquor;
(5) The preparation method of the compound of the formula I comprises the following post-treatment steps: after the iodination reaction is completed, adding a reducing agent until the color of the reaction liquid is removed, and adding water and then separating the liquid to obtain the compound of the formula I; the reducing agent is preferably sodium thiosulfate or sodium bisulfite; the reducing agent is preferably formulated as a saturated aqueous solution for use in the aftertreatment.
4. A process according to any one of claims 1 to 3, wherein in the iodination reaction n is 0 and m is Na, the molar volume ratio of the compound of formula II to the solvent is preferably 1 to 2mol/L, for example 1.16mol/L, the organic solvent is preferably an ethereal solvent, more preferably tetrahydrofuran;
alternatively, n is 1, M is K, the molar volume ratio of the compound of formula II to the solvent is preferably 0.2 to 0.3mol/L, for example 0.24mol/L, and the organic solvent is preferably an alcoholic solvent, more preferably diethylene glycol.
5. The process according to any one of claims 1 to 4, wherein the process for preparing the compound of formula I further comprises a process for preparing a compound of formula II comprising the steps of: in a solvent, carrying out reduction reaction on a compound of the formula III in the presence of a reducing agent to obtain a compound of the formula II; wherein the solvent is selected from organic solvents and water, and the organic solvents are selected from one or more of nitrile solvents, ether solvents and amide solvents;
wherein n is 0 or 1, R 1 、R 2 、R 3 And R is 4 Is as defined in any one of claims 1 to 4;
when n is 0, the reducing agent is a sodium salt reducing agent, and M is Na; when n is 1, the reducing agent is a sodium salt reducing agent or a potassium salt reducing agent, and M is corresponding Na or K.
6. The method of claim 5, wherein one or more of the following conditions are satisfied:
(1) In the reduction reaction, the molar volume ratio of the compound of formula III to the solvent is 0.2 to 1mol/L, preferably 0.4 to 0.7mol/L;
(2) In the reduction reaction, the volume ratio of the organic solvent to the water is 1:10 to 10:1, preferably 1:3 to 3:1, more preferably 1:2 to 2:1, for example 1:1 or 2:3;
(3) In the reduction reaction, in the organic solvent, the nitrile solvent is acetonitrile;
(4) In the reduction reaction, in the organic solvent, the ether solvent is selected from one or two of tetrahydrofuran and dioxane;
(5) In the reduction reaction, in the organic solvent, the amide solvent is N, N-dimethylformamide;
(6) In the reduction reaction, the molar ratio of the reducing agent to the compound of formula III is from 2:1 to 8:1, preferably from 2:1 to 5:1, for example from 2.5:1 or 3.5:1;
(7) In the reduction reaction, the sodium salt reducing agent is one or two selected from sodium sulfite and sodium tetrahydroborate, preferably sodium sulfite;
(8) In the reduction reaction, the potassium salt reducing agent is selected from one or two of potassium sulfite and potassium tetrahydroborate, preferably potassium sulfite.
7. The method of claim 5 or 6, wherein one or more of the following conditions are satisfied:
(1) In the reduction reaction, the organic solvent is selected from one or two of an ether solvent and a nitrile solvent, preferably one or more selected from tetrahydrofuran, dioxane and acetonitrile, more preferably one or two selected from tetrahydrofuran and dioxane;
(2) In the reduction reaction, n is 1, the reducing agent is the potassium salt reducing agent, and M is K;
(3) The reaction temperature of the reduction reaction is-30-160 ℃, preferably 0-80 ℃, more preferably 20-30 ℃;
(4) SO generated during the reduction reaction 2 The isogas is absorbed by alkali liquor, such as sodium hydroxide alkali liquor;
(5) The preparation method of the compound of the formula II comprises the following post-treatment steps: removing the solvent after the reduction reaction is completed, adding an organic solvent, stirring, filtering, and concentrating the obtained filtrate; the organic solvent is preferably an ester solvent, more preferably ethyl acetate.
8. The process according to claim 5 to 7,
in the reduction reaction, M is K, the reducing agent is preferably potassium sulfite, the organic solvent is preferably tetrahydrofuran, the volume ratio of the organic solvent to water is preferably 1:1, and the molar ratio of the reducing agent to the compound of the formula III is preferably 3.5:1;
alternatively, M is Na, the reducing agent is preferably sodium sulfite, the organic solvent is preferably dioxane, the volume ratio of the organic solvent to water is preferably 2:3, and the molar ratio of the reducing agent to the compound of formula III is preferably 2.5:1.
9. A compound, characterized in that the compound is a compound of formula I or a compound of formula II as shown below;
I-CF 2 CF 2 OCF 2 CF 2 -(CR 1 R 2 -CR 2 R 4 ) n -I
I
wherein n is 1, M, R 1 、R 2 、R 3 And R is 4 Is as defined in any one of claims 1 to 4;
preferably, the compound is selected from the group consisting of compound 1, compound 2, and compound 2' shown below:
10. a process for the preparation of a compound of formula II, comprising the steps of: in a solvent, carrying out reduction reaction on a compound of the formula III in the presence of a reducing agent to obtain a compound of the formula II; wherein the solvent is an organic solvent and water, and the organic solvent is one or more selected from nitrile solvents, ether solvents and amide solvents;
wherein n is 0 or 1, R 1 、R 2 、R 3 And R is 4 Is as defined in any one of claims 1 to 4;
when n is 0, the reducing agent is a sodium salt reducing agent, and M is Na; when n is 1, the reducing agent is a sodium salt reducing agent or a potassium salt reducing agent, and M is corresponding Na or K;
the other conditions and operations of the process for the preparation of the compound of formula II are preferably as defined in any one of claims 5 to 8.
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