CN105612144A - 制备模板剂的方法 - Google Patents
制备模板剂的方法 Download PDFInfo
- Publication number
- CN105612144A CN105612144A CN201480047729.2A CN201480047729A CN105612144A CN 105612144 A CN105612144 A CN 105612144A CN 201480047729 A CN201480047729 A CN 201480047729A CN 105612144 A CN105612144 A CN 105612144A
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- adamantyl
- carbonic acid
- methyl carbonic
- amines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title description 2
- -1 1- adamantylamine compound Chemical class 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 19
- IDWRJRPUIXRFRX-UHFFFAOYSA-N 3,5-dimethylpiperidine Chemical compound CC1CNCC(C)C1 IDWRJRPUIXRFRX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSOHXMFFSKTSIT-UHFFFAOYSA-N 1-adamantylmethanamine Chemical compound C1C(C2)CC3CC2CC1(CN)C3 XSOHXMFFSKTSIT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- GNUJKXOGRSTACR-UHFFFAOYSA-M 1-adamantyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C1C(C2)CC3CC2CC1([N+](C)(C)C)C3 GNUJKXOGRSTACR-UHFFFAOYSA-M 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- VKKVUEZYAULYFJ-UHFFFAOYSA-N CC(C)(CC12CC3CC(C1)CC(C3)C2)OC(=O)O Chemical compound CC(C)(CC12CC3CC(C1)CC(C3)C2)OC(=O)O VKKVUEZYAULYFJ-UHFFFAOYSA-N 0.000 claims description 2
- LLSKXGRDUPMXLC-UHFFFAOYSA-N 1-phenylpiperidine Chemical class C1CCCCN1C1=CC=CC=C1 LLSKXGRDUPMXLC-UHFFFAOYSA-N 0.000 claims 1
- FADLHVCUAWOLRZ-UHFFFAOYSA-M 1-adamantyl(trimethyl)azanium;methyl carbonate Chemical compound COC([O-])=O.C1C(C2)CC3CC2CC1([N+](C)(C)C)C3 FADLHVCUAWOLRZ-UHFFFAOYSA-M 0.000 abstract 1
- RVHXXLNTDFTAHU-UHFFFAOYSA-M COC([O-])=O.CC1CC(C)C[N+](C)(C)C1 Chemical compound COC([O-])=O.CC1CC(C)C[N+](C)(C)C1 RVHXXLNTDFTAHU-UHFFFAOYSA-M 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- KKXBPUAYFJQMLN-UHFFFAOYSA-N 1-adamantyl(trimethyl)azanium Chemical compound C1C(C2)CC3CC2CC1([N+](C)(C)C)C3 KKXBPUAYFJQMLN-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical class CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 1
- QYSPPESTBGMMOW-UHFFFAOYSA-L C([O-])([O-])=O.C12(CC3CC(CC(C1)C3)C2)C[N+](C)(C)C.C23(CC1CC(CC(C2)C1)C3)C[N+](C)(C)C Chemical class C([O-])([O-])=O.C12(CC3CC(CC(C1)C3)C2)C[N+](C)(C)C.C23(CC1CC(CC(C2)C1)C3)C[N+](C)(C)C QYSPPESTBGMMOW-UHFFFAOYSA-L 0.000 description 1
- 101100352902 Dictyostelium discoideum canA gene Proteins 0.000 description 1
- 101100379079 Emericella variicolor andA gene Proteins 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- QQZUJGFVKDKEJH-UHFFFAOYSA-N azane tert-butyl hydrogen carbonate Chemical compound N.CC(C)(C)OC(O)=O QQZUJGFVKDKEJH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 101150033714 mtcA1 gene Proteins 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- UWSCPROMPSAQOL-UHFFFAOYSA-N trimethylazanium;sulfate Chemical compound CN(C)C.CN(C)C.OS(O)(=O)=O UWSCPROMPSAQOL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/22—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of other functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
- C07D211/14—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/98—Nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
公开了一种用于制备1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓的方法。该方法包括使碳酸二甲酯与3,5-二甲基哌啶或1-金刚烷基胺化合物在水的存在下,在80至200℃的温度在密封容器中进行反应。1-金刚烷基胺化合物为1-金刚烷基胺、1-金刚烷基甲基胺或其混合物。
Description
发明领域
本发明涉及一种用于制备1-金刚烷基三甲基甲基碳酸铵和N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓的方法。
发明背景
1-金刚烷基三甲基氢氧化铵和N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓可作为生产沸石的模板剂。制备有机胺的铵盐如1-金刚烷基三甲基氢氧化铵的标准路线,包括烷基化步骤,其中有机胺与烷基化剂如硫酸二烷基酯或甲基碘反应。例如,美国专利8,252,943公开了一种用于制备铵化合物的方法,通过使含有双键氮原子的化合物与两个烷基均参与反应的硫酸二烷基酯反应,并且如果合适,使所产生的含有硫酸根阴离子的离子化合物进行阴离子交换。同样地,美国专利8,163,951教导了一种用于制备季铵化合物的方法,其包括使含有sp3杂化氮原子的化合物与硫酸二烷基酯或磷酸三烷基酯反应,以及使所产生的铵化合物进行阴离子交换。美国专利申请公布2012/0010431公开了一种用于制备1-金刚烷基三甲基氢氧化铵的方法,其包括使1-金刚烷二甲基胺与硫酸二甲酯反应以得到1-金刚烷三甲基硫酸铵,然后使其与载有OH离子的离子交换剂进行阴离子交换。此外,美国专利4,859,442在实施例1中描述了1-金刚烷基三甲基氢氧化铵的制备,通过1-金刚烷基胺与甲基碘的烷基化反应,随后再用离子交换树脂对碘阴离子进行离子交换。同样地,美国专利5,645,812教导了N,N-二乙基-3,5-二甲基氢氧化哌啶鎓模板剂的制备和使用。
此外,美国专利6,784,307教导了一种通过使具有环状碳酸酯的相应的叔胺与甲醇反应制备烷基碳酸季铵(如甲基碳酸季铵)、碳酸氢季铵和碳酸季铵的方法。ZhuoqunZheng等人在Adv.Synth.Catal.2007,349,1095-1101和中国专利申请CN1948268中描述了一种在作为催化剂的乙基甲基咪唑鎓的存在下从胺盐和碳酸二甲酯制备季盐的方法。相同作者在中国专利CN101245019中描述了没有催化剂存在下胺盐的季铵化反应。
与任何化学方法一样,需要在制备1-金刚烷基三甲基甲基碳酸铵和1-金刚烷基三甲基氢氧化铵的方法上获得更进一步的改进。我们发现了一种以高收率生产1-金刚烷基三甲基甲基碳酸铵的新方法。
发明内容
本发明是一种用于制备1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓的方法。该方法包括使碳酸二甲酯与1-金刚烷基胺化合物或3,5-二甲基哌啶在水的存在下,在80至200℃的温度在密封容器中进行反应。1-金刚烷基胺化合物为1-金刚烷基胺、1-金刚烷基甲基胺或其混合物。
发明详述
本发明的方法包括使碳酸二甲酯与1-金刚烷基胺化合物或3,5-二甲基哌啶在水的存在下,在80至200℃的温度在密封容器中进行反应。
在合并的甲基化/季铵化步骤中,使1-金刚烷基胺化合物或3,5-二甲基哌啶与碳酸二甲酯反应,以产生1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓。1-金刚烷基胺化合物为1-金刚烷基胺、1-金刚烷基甲基胺或其混合物。
优选地,1-金刚烷基胺、1-金刚烷基甲基胺或3,5-二甲基哌啶在水的存在下与碳酸二甲酯的反应在升高的温度和压力进行,例如在高压釜中。除了碳酸二甲酯、1-金刚烷基胺化合物或3,5-二甲基哌啶以及水,该反应可在其他溶剂如甲醇或其他对反应条件为惰性的非质子溶剂的存在下进行,但不需要另外的溶剂。优选地,反应步骤包括将1-金刚烷基胺化合物或3,5-二甲基哌啶与水混合,接着添加碳酸二甲酯。
通常情况下,含有3,5-二甲基哌啶或1-金刚烷基胺化合物、水和碳酸二甲酯的反应混合物在自生压力下的密封容器中在约80℃至约200℃的温度加热超过约0.25小时(优选少于约48小时)的时间。可选地,容器可以装配有用于通过排出一些产生的二氧化碳以限制压力上升的装置。更优选地,将反应混合物在约100℃至约175℃,最优选约120℃至约160℃的温度范围加热。反应温度也可以在反应过程中增加。该反应优选进行1至24小时。该反应可以使用任何适当类型的反应容器或设备,例如搅拌容器或CSTR反应器,以间歇、连续或半连续的方式进行。
优选地,碳酸二甲酯∶1-金刚烷基胺化合物或3,5-二甲基哌啶的摩尔比在5至20的范围内,更优选摩尔比在8至14的范围内。
需要存在水以使甲基化/季铵化反应进行。优选地,水∶1-金刚烷基胺化合物或3,5-二甲基哌啶的摩尔比在1至4的范围内。
反应完成后,优选回收1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓。合适的回收方法包括过滤和洗涤、旋转蒸发、离心等。在一个优选的实施方案中,将反应混合物冷却至环境温度,并且使反应混合物的一部分(优选使反应体积减小多于25%)汽提,以除去可能形成的任何甲醇。剩余的浆料可进一步冷却到低于10℃的温度,产物1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓通过过滤分离,然后用冷的碳酸二甲酯或丙酮洗涤。白色结晶产物可在真空下进一步干燥,以产生最终的1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓。
优选地,1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓进一步与氢氧化钙在水的存在下反应,以产生1-金刚烷基三甲基氢氧化铵或N,N-二甲基-3,5-二甲基哌啶氢氧化铵。除水之外,反应也可在其他溶剂如醇的存在下进行,但坏需要另外的溶剂。与1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓相比,使用至少一摩尔当量的水,但优选使用过量的水。优选相对于1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓摩尔过量的氢氧化钙,更优选氢氧化钙∶1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓的摩尔比在1.05至1.75的范围内。
优选地,氢氧化钙和1-金刚烷基三甲基甲基碳酸铵(或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓)的反应混合物在升高的温度加热,优选在回流下。将产生的甲醇缓慢蒸馏掉,直至蒸气温度恒定。
1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓本身也可以作为模板剂用于生产沸石,但优选利用1-金刚烷基三甲基氢氧化铵或N,N-二甲基-3,5-二甲基哌啶氢氧化铵。沸石合成是本领域中公知的,通常由使硅源、铝源(若需要再加上其他金属源)和模板剂在足以形成分子筛的温度和时间反应组成。典型的硅源包括胶态二氧化硅、热解法二氧化硅、醇化硅及其混合物。典型的铝源包括铝酸钠、氢氧化铝、异丙醇铝、硫酸铝和硝酸铝。
沸石合成通常在水的存在下进行。也可存在其他溶剂如醇。在形成反应混合物后,使其在足以形成分子筛的温度和时间反应。通常情况下,将反应混合物在自生压力下的密封容器中在约100℃至约250℃的温度加热超过约0.25小时(优选少于约96小时)的时间。该反应可以使用任何适当类型的反应容器或装置,例如搅拌容器或CSTR反应器,以间歇、连续或半连续的方式进行。反应完成后,回收沸石。
所合成的沸石将在孔中含有一些模板剂。可以采用任何合适的方法以除去模板剂。除去模板剂通常在含氧气体如空气或氧气和惰性气体的混合物的存在下通过高温加热进行。优选地,将沸石加热到高于250℃的温度以除去模板剂。优选约275℃至约800℃的温度。
以下实施例仅说明本发明。本领域的技术人员将认识到在本发明的主旨和权利要求书的范围内的许多变化。
实施例1:制备1-金刚烷基三甲基氢氧化铵
金刚烷基三甲基甲基碳酸铵的合成:将1-金刚烷基胺(37.7g,0.25mol)、碳酸二甲酯(300mL,3.5mol)和水(9mL,0.5mol)在高压釜中合并,并加热至150℃持续10小时。该高压釜装有压力释放,使得能达到的最大压力为10巴(1000kPa)。冷却时,容器的内容物被汽提完全干燥,残余物用150mL丙酮制浆,冷却,过滤,并用少量冷的丙酮洗涤。干燥得到54g(80.6%)的收率,H-NMR分析与结构一致。
1-金刚烷基三甲基氢氧化铵的合成:将金刚烷基三甲基甲基碳酸铵(383g,1.42mol)添加到水(1000mL)中,随后添加氢氧化钙(148g,2.0mol)。该添加是放热的。然后将反应混合物加热至回流,将产生的甲醇缓慢蒸馏掉,直至蒸气温度恒定。然后将反应混合物缓慢冷却至10℃,并将沉淀的碳酸钙和过量的氢氧化钙用吸滤器(Nutschefilter)滤除。滤饼用水(200mL)洗涤,并且将母液和洗涤滤液合并。1-金刚烷基三甲基氢氧化铵产物的收率为根据分析20.2%w/w的1284g溶液。
实施例2:制备1-金刚烷基三甲基氢氧化铵
将1-金刚烷基胺(30.2g,0.2mol)、碳酸二甲酯(250mL)、甲醇(25mL)和水(4.5g,0.25mol)在高压釜中合并,并在140℃加热8小时。将容器冷却,并将内容物汽提至干燥。粗产物收率为51g(94.6%)。将该1-金刚烷基三甲基甲基碳酸铵粗产物直接用于下一步骤。
将前一反应得到的甲基碳酸酯盐粗产物溶解在150mL去离子水中,过滤掉少量固体,并用另外的25mL去离子水洗涤。然后将滤液转移到设置用于蒸馏的烧瓶中,并添加21g氢氧化钙。将混合物加热至沸腾,并将甲醇和少量蒸汽以及挥发性有机物质蒸馏出。在冷却时,滤除不溶性钙盐,并用少量去离子水洗涤。1-金刚烷基三甲基氢氧化铵溶液的产物的收率为根据分析16.0%的204g(总体77%)。
实施例3:制备N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓
将3,5-二甲基哌啶(28.2g,0.25mol)、碳酸二甲酯(300mL)和水(9g,0.5mol)在高压釜中合并,并加热至150℃持续6小时。该高压釜装有压力释放,使得所达到的最大压力为6巴(600kPa)。将容器的内容物汽提至干燥,然后将150mL丙酮添加到该混合物中,在10℃下搅拌,然后过滤,得到所需的N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓盐(38g,70%)。H-NMR分析与结构一致。如实施例1中所述,该物质可与氢氧化钙转化为氢氧化物盐。
虽然本发明的方法成功地生产1-金刚烷基三甲基甲基碳酸铵和N,N-二甲基-3,5-二甲基甲基碳酸哌啶鎓,但是当施加到单烷基伯胺如正十二烷基胺或苄胺时,该方法令人惊奇地不太成功,得到各种副产品和仅低收率的所需的甲基碳酸季盐。
Claims (11)
1.用于制备1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶的方法,该方法包括使碳酸二甲酯与3,5-二甲基哌啶或1-金刚烷基胺化合物在水的存在下,在80至200℃的温度在密封容器中进行反应,其中1-金刚烷基胺化合物选自1-金刚烷基胺、1-金刚烷基甲基胺及其混合物。
2.根据权利要求1所述的方法,其中碳酸二甲酯:1-金刚烷基胺化合物或3,5-二甲基哌啶的摩尔比在5至20范围内。
3.根据权利要求1所述的方法,其中碳酸二甲酯:1-金刚烷基胺化合物或3,5-二甲基哌啶的摩尔比在8至14范围内。
4.根据权利要求1所述的方法,其中水:1-金刚烷基胺化合物或3,5-二甲基哌啶的摩尔比在1至4范围内。
5.根据权利要求1所述的方法,其中1-金刚烷基胺化合物或3,5-二甲基哌啶与碳酸二甲酯的反应在120-160℃范围内的温度进行。
6.根据权利要求1所述的方法,其中1-金刚烷基胺化合物为1-金刚烷基胺。
7.根据权利要求1所述的方法,还包括使1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶与氢氧化钙在水的存在下反应,以产生1-金刚烷基三甲基氢氧化铵。
8.根据权利要求7所述的方法,其中氢氧化钙:1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶的摩尔比率在1.05至1.75范围内。
9.根据权利要求7所述的方法,其中1-金刚烷基三甲基甲基碳酸铵或N,N-二甲基-3,5-二甲基甲基碳酸哌啶与氢氧化钙在水的存在下的反应在回流下进行。
10.根据权利要求1所述的方法,其中碳酸二甲酯与3,5-二甲基哌啶反应,以产生N,N-二甲基-3,5-二甲基甲基碳酸哌啶
11.根据权利要求1所述的方法,其中碳酸二甲酯与1-金刚烷基胺反应,以产生1-金刚烷基三甲基甲基碳酸铵。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811355939.4A CN109293517A (zh) | 2013-08-28 | 2014-08-28 | 制备模板剂的方法 |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361870973P | 2013-08-28 | 2013-08-28 | |
US61/870,973 | 2013-08-28 | ||
PCT/IB2014/064132 WO2015028971A1 (en) | 2013-08-28 | 2014-08-28 | Method of making a templating agent |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811355939.4A Division CN109293517A (zh) | 2013-08-28 | 2014-08-28 | 制备模板剂的方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105612144A true CN105612144A (zh) | 2016-05-25 |
Family
ID=51542413
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201480047729.2A Pending CN105612144A (zh) | 2013-08-28 | 2014-08-28 | 制备模板剂的方法 |
CN201811355939.4A Pending CN109293517A (zh) | 2013-08-28 | 2014-08-28 | 制备模板剂的方法 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811355939.4A Pending CN109293517A (zh) | 2013-08-28 | 2014-08-28 | 制备模板剂的方法 |
Country Status (10)
Country | Link |
---|---|
US (2) | US9321723B2 (zh) |
EP (1) | EP3039007A1 (zh) |
JP (1) | JP6794256B2 (zh) |
KR (2) | KR102299906B1 (zh) |
CN (2) | CN105612144A (zh) |
BR (1) | BR112016003940B1 (zh) |
DE (1) | DE102014112363B4 (zh) |
GB (2) | GB2522093B (zh) |
RU (1) | RU2680406C2 (zh) |
WO (1) | WO2015028971A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113321587A (zh) * | 2021-06-30 | 2021-08-31 | 肯特催化材料股份有限公司 | 一种金刚烷基三甲基氢氧化铵的制备方法及其制备的季铵碱水溶液 |
CN113845125A (zh) * | 2021-10-11 | 2021-12-28 | 南京华洲新材料有限公司 | 3,5-二甲基哌啶鎓盐模板剂及分子筛的合成方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2542876B (en) * | 2015-04-20 | 2019-10-23 | Johnson Matthey Plc | Structure Directing Agent |
GB201810449D0 (en) | 2018-06-26 | 2018-08-08 | Johnson Matthey Plc | Hydrogenation process |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0291074A2 (en) * | 1987-05-13 | 1988-11-17 | Mitsubishi Petrochemical Co., Ltd. | Process for producing quaternary salts |
JP2010138087A (ja) * | 2008-12-10 | 2010-06-24 | Tosoh Corp | N,n,n−トリアルキルアダマンタンアンモニウムアルキルカーボネートの製造方法 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2651984C2 (de) * | 1976-11-15 | 1983-01-27 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von N,N-Dimethylpiperidiniumchlorid oder N,N-Dimethylmorpholiniumchlorid |
US4859442A (en) | 1986-01-29 | 1989-08-22 | Chevron Research Company | Zeolite SSZ-23 |
US5789614A (en) * | 1987-01-13 | 1998-08-04 | Daicel Chemical Industries, Ltd. | Process for preparation of aliphatic diisocyanate compounds |
US5192726A (en) * | 1991-09-03 | 1993-03-09 | Uop | Beidellite clay and process for preparing the clay |
US5645812A (en) | 1993-10-01 | 1997-07-08 | Chevron U.S.A. Inc. | Zeolite ZSM-11 and a process for preparing zeolite ZSM-11 using a 3,5-dimethylpiperidinium templating agent |
US5968474A (en) * | 1994-09-30 | 1999-10-19 | Chevron U.S.A. Inc. | Pure phase titanium-containing zeolite having MEL structure, process for preparing same, and oxidation processes using same as catalyst |
US5958370A (en) * | 1997-12-11 | 1999-09-28 | Chevron U.S.A. Inc. | Zeolite SSZ-39 |
US6288009B1 (en) * | 1998-04-10 | 2001-09-11 | Basf Corporation | Plant growth regulator compositions |
JP2002302405A (ja) * | 2001-03-30 | 2002-10-18 | Sanyo Chem Ind Ltd | 粉末状抗菌剤組成物 |
UA76478C2 (uk) | 2001-07-09 | 2006-08-15 | Лонза Інк. | Способи одержання алкілкарбонатів четвертинного амонію in situ |
JP4300407B2 (ja) * | 2003-04-11 | 2009-07-22 | 三菱瓦斯化学株式会社 | 水酸化テトラアルキルアンモニウムの製造方法 |
DE102004010662A1 (de) | 2004-03-04 | 2005-09-22 | Basf Ag | Verfahren zur Herstellung von Verbindungen mit quaternären sp2-hybridisierten Stickstoffatomen |
KR20070015441A (ko) | 2004-05-28 | 2007-02-02 | 바스프 악티엔게젤샤프트 | 4차 암모늄 화합물의 제조 방법 |
CN1948268A (zh) | 2005-10-10 | 2007-04-18 | 浙江师范大学 | 季铵盐的合成方法 |
CN101245019B (zh) | 2007-02-14 | 2011-04-20 | 邱建兴 | 季铵盐合成新工艺 |
JP2010116349A (ja) * | 2008-11-13 | 2010-05-27 | Tosoh Corp | 新規なn,n,n−トリメチル−1−アダマンタンアンモニウムメチルカーボネート |
JP5689078B2 (ja) | 2009-03-12 | 2015-03-25 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 1−アダマンチルトリメチルアンモニウム水酸化物の製造方法 |
JP5428501B2 (ja) * | 2009-04-28 | 2014-02-26 | 東ソー株式会社 | ゼオライト製造用の構造指向剤 |
CN101935286A (zh) * | 2009-06-26 | 2011-01-05 | 出光兴产株式会社 | 具有金刚烷基的季铵盐的制备方法 |
CN101993377A (zh) * | 2009-08-07 | 2011-03-30 | 出光兴产株式会社 | 具有金刚烷骨架的胺类和季铵盐的制造方法 |
JP2011051976A (ja) * | 2009-08-07 | 2011-03-17 | Idemitsu Kosan Co Ltd | アダマンタン骨格を有するアミン類及び第4級アンモニウム塩の製造方法 |
BR112015024535B1 (pt) * | 2013-03-27 | 2021-01-12 | Johnson Matthey Public Limited Company | Método para preparar hidróxido de 1-adamantiltrimetil amônio |
-
2014
- 2014-08-28 RU RU2016111130A patent/RU2680406C2/ru active
- 2014-08-28 GB GB1415212.8A patent/GB2522093B/en active Active
- 2014-08-28 KR KR1020217017377A patent/KR102299906B1/ko active IP Right Grant
- 2014-08-28 CN CN201480047729.2A patent/CN105612144A/zh active Pending
- 2014-08-28 BR BR112016003940-8A patent/BR112016003940B1/pt not_active IP Right Cessation
- 2014-08-28 KR KR1020167007725A patent/KR102272178B1/ko active IP Right Grant
- 2014-08-28 CN CN201811355939.4A patent/CN109293517A/zh active Pending
- 2014-08-28 EP EP14766543.4A patent/EP3039007A1/en not_active Withdrawn
- 2014-08-28 GB GB1616031.9A patent/GB2540066B/en active Active
- 2014-08-28 WO PCT/IB2014/064132 patent/WO2015028971A1/en active Application Filing
- 2014-08-28 DE DE102014112363.8A patent/DE102014112363B4/de active Active
- 2014-08-28 JP JP2016537418A patent/JP6794256B2/ja active Active
- 2014-08-28 US US14/471,737 patent/US9321723B2/en active Active
-
2016
- 2016-03-04 US US15/060,979 patent/US9656946B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0291074A2 (en) * | 1987-05-13 | 1988-11-17 | Mitsubishi Petrochemical Co., Ltd. | Process for producing quaternary salts |
JP2010138087A (ja) * | 2008-12-10 | 2010-06-24 | Tosoh Corp | N,n,n−トリアルキルアダマンタンアンモニウムアルキルカーボネートの製造方法 |
Non-Patent Citations (1)
Title |
---|
PAUL WAGNER, ET AL.: ""Guest/Host Relationships in the Synthesis of the Novel Cage-Based Zeolites SSZ-35, SSZ-36, and SSZ-39"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113321587A (zh) * | 2021-06-30 | 2021-08-31 | 肯特催化材料股份有限公司 | 一种金刚烷基三甲基氢氧化铵的制备方法及其制备的季铵碱水溶液 |
CN113321587B (zh) * | 2021-06-30 | 2022-05-17 | 肯特催化材料股份有限公司 | 一种金刚烷基三甲基氢氧化铵的制备方法及其制备的季铵碱水溶液 |
CN113845125A (zh) * | 2021-10-11 | 2021-12-28 | 南京华洲新材料有限公司 | 3,5-二甲基哌啶鎓盐模板剂及分子筛的合成方法 |
Also Published As
Publication number | Publication date |
---|---|
BR112016003940B1 (pt) | 2020-12-29 |
GB201616031D0 (en) | 2016-11-02 |
KR20210070405A (ko) | 2021-06-14 |
US20160185709A1 (en) | 2016-06-30 |
KR20160048869A (ko) | 2016-05-04 |
GB201415212D0 (en) | 2014-10-15 |
GB2540066B (en) | 2017-06-14 |
CN109293517A (zh) | 2019-02-01 |
RU2016111130A (ru) | 2017-10-03 |
RU2680406C2 (ru) | 2019-02-21 |
US20150065718A1 (en) | 2015-03-05 |
RU2016111130A3 (zh) | 2018-05-31 |
RU2019103865A3 (zh) | 2022-01-18 |
RU2019103865A (ru) | 2019-04-09 |
KR102272178B1 (ko) | 2021-07-05 |
JP2016530276A (ja) | 2016-09-29 |
JP6794256B2 (ja) | 2020-12-02 |
GB2522093B (en) | 2016-12-28 |
EP3039007A1 (en) | 2016-07-06 |
DE102014112363B4 (de) | 2015-10-22 |
GB2540066A (en) | 2017-01-04 |
US9321723B2 (en) | 2016-04-26 |
US9656946B2 (en) | 2017-05-23 |
DE102014112363A1 (de) | 2015-03-05 |
KR102299906B1 (ko) | 2021-09-09 |
GB2522093A (en) | 2015-07-15 |
WO2015028971A1 (en) | 2015-03-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109438260A (zh) | 1-金刚烷基三甲基氢氧化铵的制备方法 | |
CN105612144A (zh) | 制备模板剂的方法 | |
JP2005511803A (ja) | メチルセルロースエーテルの製造のための方法 | |
JP3644051B2 (ja) | 塩基性酢酸アルミニウム水溶液の製造方法 | |
JP4107715B2 (ja) | イミダゾリウム系溶融塩型電解質の調製方法 | |
JP6051757B2 (ja) | イオン液体 | |
JPH0212469B2 (zh) | ||
CN105949094B (zh) | 二[4‑(2‑羟基乙氧基)苯基]砜及其衍生物的制备方法及其催化剂 | |
JPH07187666A (ja) | ベーマイトの製造方法 | |
RU2775223C2 (ru) | Способ получения шаблонного реагента | |
JP6387138B2 (ja) | スピロ4級アンモニウム塩の製造方法 | |
KR101488781B1 (ko) | 염료 감응형 태양전지 전해질용 고순도 이온성 액체 제조방법 및 이 방법에 의해 제조되는 염료 감응형 태양전지 전해질용 고순도 이온성 액체 | |
JPH04122728A (ja) | エーテル化ポリオキシアルキレン化合物の製造方法 | |
CN111978154A (zh) | 一种4-辛基苯乙醇的制备方法 | |
JPS6021586B2 (ja) | 2−ピロリドン−5−カルボン酸アルミニウム塩の製造方法 | |
JPS6330453A (ja) | 四級アンモニウムヨウ化物のアニオン交換方法 | |
JP2017200889A (ja) | イオン液体の製造方法及びイオン液体製造のための中間体の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160525 |
|
RJ01 | Rejection of invention patent application after publication |