JP4586200B2 - Quaternary ammonium salt supported on magnetic fine particles, production method thereof, magnetic fine particle-supported phase transfer catalyst comprising the same, and phase transfer reaction using the same - Google Patents
Quaternary ammonium salt supported on magnetic fine particles, production method thereof, magnetic fine particle-supported phase transfer catalyst comprising the same, and phase transfer reaction using the same Download PDFInfo
- Publication number
- JP4586200B2 JP4586200B2 JP2006131902A JP2006131902A JP4586200B2 JP 4586200 B2 JP4586200 B2 JP 4586200B2 JP 2006131902 A JP2006131902 A JP 2006131902A JP 2006131902 A JP2006131902 A JP 2006131902A JP 4586200 B2 JP4586200 B2 JP 4586200B2
- Authority
- JP
- Japan
- Prior art keywords
- magnetic fine
- fine particles
- phase transfer
- ammonium salt
- quaternary ammonium
- 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.)
- Expired - Fee Related
Links
- 239000010419 fine particle Substances 0.000 title claims description 55
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000006276 transfer reaction Methods 0.000 title claims description 16
- 239000003444 phase transfer catalyst Substances 0.000 title claims description 14
- 239000003054 catalyst Substances 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 3
- 125000005369 trialkoxysilyl group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 238000006243 chemical reaction Methods 0.000 description 29
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 150000002430 hydrocarbons Chemical group 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000010908 decantation Methods 0.000 description 8
- 229910001172 neodymium magnet Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000000696 magnetic material Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 230000005389 magnetism Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000002367 halogens Chemical group 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NILZGRNPRBIQOG-UHFFFAOYSA-N 3-iodopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCI NILZGRNPRBIQOG-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229940107816 ammonium iodide Drugs 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- IEVOYZVDTPGWJB-UHFFFAOYSA-M triethyl(3-trimethoxysilylpropyl)azanium;iodide Chemical compound [I-].CC[N+](CC)(CC)CCC[Si](OC)(OC)OC IEVOYZVDTPGWJB-UHFFFAOYSA-M 0.000 description 3
- BIGOJJYDFLNSGB-UHFFFAOYSA-N 3-isocyanopropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCC[N+]#[C-] BIGOJJYDFLNSGB-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- BEJFPMHAIRMHAS-UHFFFAOYSA-M [I-].C(CCC)[N+](CCC[Si](OC)(OC)OC)(CCCC)CCCC Chemical compound [I-].C(CCC)[N+](CCC[Si](OC)(OC)OC)(CCCC)CCCC BEJFPMHAIRMHAS-UHFFFAOYSA-M 0.000 description 2
- CCFAFCAVKMEQLJ-UHFFFAOYSA-M [I-].C(CCCCCC)[N+](CCC[Si](OC)(OC)OC)(CCCCCCC)CCCCCCC Chemical compound [I-].C(CCCCCC)[N+](CCC[Si](OC)(OC)OC)(CCCCCCC)CCCCCCC CCFAFCAVKMEQLJ-UHFFFAOYSA-M 0.000 description 2
- IXZCVHCLWTZVJA-UHFFFAOYSA-M [I-].C(CCCCCCC)[N+](CCC[Si](OC)(OC)OC)(CCCCCCCC)CCCCCCCC Chemical compound [I-].C(CCCCCCC)[N+](CCC[Si](OC)(OC)OC)(CCCCCCCC)CCCCCCCC IXZCVHCLWTZVJA-UHFFFAOYSA-M 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical compound CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- FRLRKOBIHDUBMS-UHFFFAOYSA-N tributylazanium;iodide Chemical compound [I-].CCCC[NH+](CCCC)CCCC FRLRKOBIHDUBMS-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010702 ether synthesis reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CLZGJKHEVKJLLS-UHFFFAOYSA-N n,n-diheptylheptan-1-amine Chemical compound CCCCCCCN(CCCCCCC)CCCCCCC CLZGJKHEVKJLLS-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QAJGUMORHHJFNJ-UHFFFAOYSA-M sodium;phenoxide;trihydrate Chemical compound O.O.O.[Na+].[O-]C1=CC=CC=C1 QAJGUMORHHJFNJ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- KKCMQLNSFDDSSD-UHFFFAOYSA-M tripentyl(3-trimethoxysilylpropyl)azanium iodide Chemical compound [I-].CCCCC[N+](CCCCC)(CCCCC)CCC[Si](OC)(OC)OC KKCMQLNSFDDSSD-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
本発明は、分離回収が容易で尚且つ再利用可能な新規４級アンモニウム塩とその製造方法、並びに前記磁性微粒子担持４級アンモニウム塩からなる相間移動触媒、及びそれを用いた相間移動反応に関する。 The present invention relates to a novel quaternary ammonium salt that is easy to separate and recover and can be reused, a method for producing the same, a phase transfer catalyst comprising the quaternary ammonium salt carrying magnetic fine particles, and a phase transfer reaction using the same.
相間移動反応は環境調和型の有機合成反応としてその有用性が認識され、広く研究されているだけでなく、多くの化合物の工業的製法にも応用されている。しかしながら、相間移動反応の触媒として用いられる４級アンモニウム塩等は反応後の分離回収が困難な為、触媒の再利用ができないことが問題となっている。そこで、反応終了後の分離回収が容易で尚且つ再利用可能な相間移動触媒の開発が求められている。 Phase transfer reactions have been recognized for their usefulness as environmentally conscious organic synthesis reactions and are not only widely studied but also applied to the industrial production of many compounds. However, since quaternary ammonium salts and the like used as phase transfer reaction catalysts are difficult to separate and recover after the reaction, there is a problem that the catalyst cannot be reused. Therefore, development of a phase transfer catalyst that is easy to separate and recover after completion of the reaction and can be reused is required.
上記の問題を解決する手段として、相間移動触媒をポリマーに担持させることによって、ろ過による触媒の分離回収を可能にする方法が提案されている。例えば、非特許文献１、２にはポリスチレン上に担持された４級アンモニウム塩を用いる相間移動反応が記載されている。しかしながら、ポリマーを担体として用いることで、有機溶媒による膨潤の為に使用できる溶媒が限定されることや操作性が悪化すること、物理的に壊れやすいこと、熱安定性が悪いこと等の新たな問題点が生まれる。 As a means for solving the above-described problem, a method has been proposed in which a phase transfer catalyst is supported on a polymer so that the catalyst can be separated and recovered by filtration. For example, Non-Patent Documents 1 and 2 describe a phase transfer reaction using a quaternary ammonium salt supported on polystyrene. However, by using a polymer as a carrier, new solvents such as limited solvents that can be used for swelling with organic solvents, poor operability, physical fragility, poor thermal stability, etc. Problems are born.
一方、マグネタイトやフェライト等の磁性材料はナノサイズの微粒子が製造可能であり、その表面に機能性有機分子を担持させることも可能である。例えば特許文献１、２にはナノサイズの磁性微粒子に担持された生理活性物質や酵素の製造方法が記載されている。しかも、これらの磁性微粒子は無機材料である為、有機溶媒による膨潤も起きず、ポリマー粒子と比べて熱的にも物理的にも安定であることが予想される。更に、磁気により迅速に分離回収することが可能であるというポリマーには無い最大の特徴を有している。
しかしながら、これらの特許文献において磁性微粒子に担持されるものは生理活性物質や酵素にすぎず、相間移動触媒については未だに知られていないのが現状である。
However, in these patent documents, what is supported on magnetic fine particles is only a physiologically active substance or an enzyme, and the phase transfer catalyst is not yet known at present.
本発明は上記に挙げた従来技術の問題点を克服する為になされたものであって、４級アンモニウム塩を磁性微粒子に担持させることで、磁気による分離回収が可能で尚且つ再利用も可能な相間移動触媒を提供することを目的とするものである。 The present invention has been made to overcome the above-mentioned problems of the prior art, and by supporting a quaternary ammonium salt on magnetic fine particles, it can be separated and recovered by magnetism and can also be reused. An object of the present invention is to provide a simple phase transfer catalyst.
本発明者らは、前記課題を解決する為に鋭意研究を重ねた結果、磁性微粒子に相間移動触媒を固定化することによって、触媒が磁気により操作可能となるため、反応後の触媒の分離回収および再利用が大幅に簡便になるに想到し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have made it possible to operate the catalyst magnetically by immobilizing the phase transfer catalyst on the magnetic fine particles, so that the catalyst can be separated and recovered after the reaction. As a result, the present invention has been completed.
すなわち、本発明によれば、以下の発明が提供される。
（１）磁性体微粒子上に、下記の一般式（１）
That is, according to the present invention, the following inventions are provided.
(1) On the magnetic fine particles, the following general formula (1)
（式中、Ｒ１は炭化水素基を表す。Ｒ２、Ｒ３、Ｒ４は炭化水素基を表し、それぞれが結合して環を形成していてもよい。Ｘ−は酸の陰イオンを表す。）で表される４級アンモニウム塩部位を有するシロキシ基が結合していることを特徴とする磁性微粒子担持４級アンモニウム塩。
（２）下記の一般式（２）
(In the formula, R 1 represents a hydrocarbon group. R 2 , R 3 , and R 4 each represents a hydrocarbon group, which may be bonded to each other to form a ring. X − represents an anion of an acid. A magnetic fine particle-supported quaternary ammonium salt, wherein a siloxy group having a quaternary ammonium salt moiety represented by formula (1) is bonded.
(2) The following general formula (2)
（式中、Ｒ１は炭化水素基を表す。Ｒ２、Ｒ３、Ｒ４は炭化水素基を表し、それぞれが結合して環を形成していてもよい。Ｒ５は炭素数が１から３のアルキル基を表す。Ｘ−は酸の陰イオンを表す。）で表されるトリアルコキシシリル基を有する４級アンモニウム塩と磁性微粒子を反応させることを特徴とする上記（１）の磁性微粒子担持４級アンモニウム塩の製造方法。
（３）上記（１）の磁性微粒子担持４級アンモニウム塩からなることを特徴とする相間移動触媒。
（４）上記（１）の磁性微粒子担持４級アンモニウム塩を触媒に用いることを特徴とする相間移動反応。
(In the formula, R 1 represents a hydrocarbon group. R 2 , R 3 , and R 4 each represents a hydrocarbon group, which may be bonded to each other to form a ring. R 5 has 1 carbon number. Wherein the magnetic fine particles are reacted with a quaternary ammonium salt having a trialkoxysilyl group represented by the formula (1), wherein X − represents an anion of an acid. A method for producing a supported quaternary ammonium salt.
(3) A phase transfer catalyst comprising the quaternary ammonium salt carrying the magnetic fine particles of (1) above.
(4) A phase transfer reaction characterized in that the magnetic fine particle supported quaternary ammonium salt of (1) is used as a catalyst.
本発明によれば、磁気操作可能な磁性微粒子担持４級アンモニウム塩を得ることができる。こうして得られた磁性微粒子担持４級アンモニウム塩を相間移動触媒として用いることにより、相間移動反応を有効に進めることができるだけでなく、触媒の迅速且つ簡便な分離回収と再使用が可能となる。 According to the present invention, a magnetic fine particle-supported quaternary ammonium salt that can be magnetically operated can be obtained. By using the magnetic particle-supported quaternary ammonium salt thus obtained as a phase transfer catalyst, not only can the phase transfer reaction proceed effectively, but the catalyst can be quickly and easily separated and recovered and reused.
本ハツメイニヨリ得られる、新規な磁性微粒子担持４級アンモニウム塩は、磁性微粒子上に、前記一般式（１）で表される４級アンモニウム塩部位を有するシロキシ基が結合しているものであって、下記のとおり表される。 The novel magnetic fine particle-supported quaternary ammonium salt obtained by the present fluffy tail is obtained by binding a siloxy group having a quaternary ammonium salt moiety represented by the general formula (1) on the magnetic fine particle, It is expressed as follows.
（式中、Ｍは磁性微粒子を表し、磁性微粒子Ｒ１炭化水素基を表す。Ｒ２、Ｒ３、Ｒ４は炭化水素基を表し、それぞれが結合して環を形成していてもよい。Ｘ−は酸の陰イオンを表す。）
以下、上記［化５］で表される磁性微粒子担持４級アンモニウム塩について、その詳細を具体的に記述する。
Ｍは磁性微粒子を表す。本発明で担体として用いる磁性微粒子の種類には特に制限が無く、マグネタイト、フェライト、マグヘマイト等、公知のものであれば如何なるものでも使用できる。
本発明における磁性微粒子は如何なる大きさものでも使用可能であるが、小さすぎると磁気によって回収する事が困難となり、大きすぎても触媒効率が低下する為、１００ｎｍから１００μｍの粒径を有するものが好ましい。
(In the formula, M represents a magnetic fine particle and represents a magnetic fine particle R 1 hydrocarbon group. R 2 , R 3 , and R 4 represent a hydrocarbon group, and each may be bonded to form a ring. X - represents an anion of acid).
Hereinafter, the details of the magnetic fine particle-supported quaternary ammonium salt represented by the above [Chemical Formula 5] will be specifically described.
M represents magnetic fine particles. The type of magnetic fine particles used as a carrier in the present invention is not particularly limited, and any known magnetic particles such as magnetite, ferrite, maghemite, etc. can be used.
The magnetic fine particles of any size can be used in the present invention, but if they are too small, it is difficult to recover them by magnetism, and if they are too large, the catalyst efficiency decreases, so those having a particle diameter of 100 nm to 100 μm. preferable.
Ｒ１は、炭化水素基であり、アルキレン基、芳香環上に置換基を有する或は有しないアリール基の中から選ばれる。具体的には、メチレン基、エチレン基、プロピレン基、ブチレン基、フェニル基、ナフチル基、ビフェニル基、ビナフチル基等が挙げられる。
また、Ｒ２、Ｒ３、Ｒ４は、炭化水素基であり、それぞれが結合して環を形成していてもよく、アルキル基、アルキレン基、アラルキル基、芳香環上に置換基を有する或は有しないアリール基の中から選ばれる。具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、イソプロピル基、イソブチル基、シクロペンチル基、シクロヘキシル基、メチレン基、エチレン基、プロピレン基、ブチレン基、ベンジル基、フェネチル基、フェニル基、ナフチル基、ビフェニル基、ビナフチル基等が挙げられる。
さらに、Ｘ−は酸の陰イオンを表す。好ましいものとして、具体的にはＦ−、Ｃｌ−、Ｂｒ−、Ｉ−のハロゲンイオンの他、ＯＨ−、ＨＳＯ４ −、ＮＯ３ −、（ＣＦ３ＳＯ２）２Ｎ−、ＣＦ３ＳＯ３ −、（ＣＦ３ＳＯ２）３Ｃ−、ＰＦ６ −、ＢＦ４ −等が挙げられるが、これらに限られるものではない。
R 1 is a hydrocarbon group, and is selected from an alkylene group and an aryl group with or without a substituent on the aromatic ring. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a phenyl group, a naphthyl group, a biphenyl group, and a binaphthyl group.
R 2 , R 3 and R 4 are hydrocarbon groups which may be bonded to each other to form a ring, and have a substituent on the alkyl group, alkylene group, aralkyl group or aromatic ring; Is selected from aryl groups that do not have. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, cyclopentyl group, cyclohexyl group, methylene group, ethylene group, propylene group, Examples include butylene group, benzyl group, phenethyl group, phenyl group, naphthyl group, biphenyl group, and binaphthyl group.
Further, X − represents an anion of an acid. Preferable examples include, specifically, F − , Cl − , Br − and I − halogen ions, OH − , HSO 4 − , NO 3 − , (CF 3 SO 2 ) 2 N − and CF 3 SO 3. -, (CF 3 SO 2) 3 C -, PF 6 -, BF 4 - and others as mentioned, is not limited thereto.
次に、本発明の磁性微粒子担持４級アンモニウム塩の製造方法について以下に記述する。
上記の本発明の磁性微粒子担持４級アンモニウム塩は、下記の一般式（２）
Next, a method for producing the magnetic fine particle supported quaternary ammonium salt of the present invention will be described below.
The magnetic fine particle-supported quaternary ammonium salt of the present invention has the following general formula (2)
（式中、Ｒ１は炭化水素基を表す。Ｒ２、Ｒ３、Ｒ４は炭化水素基を表し、それぞれが結合して環を形成していてもよい。Ｒ５は炭素数が１から３のアルキル基を表す。Ｘ−は酸の陰イオンを表す。）で表されるトリアルコキシシリル基を有する４級アンモニウム塩と磁性微粒子とを溶媒中で反応させることにより得ることができる。 (In the formula, R 1 represents a hydrocarbon group. R 2 , R 3 , and R 4 each represents a hydrocarbon group, which may be bonded to each other to form a ring. R 5 has 1 carbon number. represents the 3 alkyl groups .X - it can be obtained by reacting the quaternary ammonium salt and the magnetic fine particles having a trialkoxysilyl group represented by represents) an anion of an acid in a solvent..
この反応に使用できる溶媒は原料となる一般式（２）で表されるアンモニウム塩を溶解し得るものであれば特に制限は無く、具体的にはエタノール、メタノール、１−プロパノール、２−プロパノール、クロロホルム、ジクロロメタン、ジクロロエタン等が挙げられる。これらの溶媒は単独での使用に限られず、適宜混合して用いてもよい。また、この反応では有機溶媒に対して０．５〜１％の水の添加で反応が促進される場合もある。 The solvent that can be used for this reaction is not particularly limited as long as it can dissolve the ammonium salt represented by the general formula (2) as a raw material. Specifically, ethanol, methanol, 1-propanol, 2-propanol, Examples include chloroform, dichloromethane, dichloroethane and the like. These solvents are not limited to being used alone, and may be used by appropriately mixing them. In this reaction, the reaction may be promoted by adding 0.5 to 1% of water with respect to the organic solvent.
反応条件としては、反応温度が低すぎると反応が進行しにくく、また、高すぎても好ましくない副反応が起こる可能性があることから、０℃から１５０℃の範囲が好ましく、更に好ましくは２５℃から１２０℃の範囲である。又、反応時間は一概に定める事はできないが、通常は１２時間〜２４時間で十分である。 The reaction conditions are preferably in the range of 0 ° C. to 150 ° C., more preferably 25, because the reaction is difficult to proceed if the reaction temperature is too low, and undesirable side reactions may occur if the reaction temperature is too high. It is in the range of from ° C to 120 ° C. The reaction time cannot be generally determined, but usually 12 hours to 24 hours is sufficient.
本発明においては、原料となる一般式（２）で表される４級アンモニウム塩と磁性微粒子の使用割合に特に制限はないが、磁性微粒子に対して原料となるアンモニウム塩の割合が少なすぎると担持量が減少し、また大量に使用しすぎても製造コストの無駄につながる恐れが有る事から、磁性微粒子１モル当たり０．５〜５モルの範囲の４級アンモニウム塩を用いることが好ましい。 In the present invention, there is no particular limitation on the use ratio of the quaternary ammonium salt represented by the general formula (2) as a raw material and magnetic fine particles, but if the proportion of the ammonium salt as a raw material is too small relative to the magnetic fine particles, It is preferable to use a quaternary ammonium salt in the range of 0.5 to 5 moles per mole of magnetic fine particles, because the supported amount decreases and there is a possibility that the production cost is wasted even if it is used in a large amount.
本発明の磁性微粒子担持４級アンモニウム塩を相間移動触媒として用いることにより、各種の相間移動反応を進行させることができる。具体的にはハロゲン交換反応、脱ハロゲン化水素反応、エーテル合成反応、シアノ化反応、酸化反応等が挙げられる。以下にこれらの中の反応例について示す。なお、本発明の前記磁性微粒子担持４級アンモニウム塩は前記した相間移動反応に用いることができるものであり、相間移動反応であれば、ここに挙げられる相間移動反応以外の相間移動反応にも使用することができる。 By using the magnetic fine particle-supported quaternary ammonium salt of the present invention as a phase transfer catalyst, various phase transfer reactions can proceed. Specific examples include a halogen exchange reaction, a dehydrohalogenation reaction, an ether synthesis reaction, a cyanation reaction, and an oxidation reaction. The reaction examples among these are shown below. The magnetic fine particle-supported quaternary ammonium salt of the present invention can be used for the phase transfer reaction described above. If the phase transfer reaction is used, it is also used for a phase transfer reaction other than the phase transfer reaction listed here. can do.
上記［化５］で表される本発明の磁性微粒子担持４級アンモニウム塩を触媒として用いることにより、以下の反応を行うことができる。
すなわち、前記触媒の存在下に、下記一般式（３）
Ｒ６−Ｘ２ （３）
(式中Ｒ６は炭化水素基を表し、炭素数１〜２０のアルキル基、ベンジル基から選ばれるいずれの基でもよい。Ｘ２はＦ、Ｃｌ、Ｂｒ、Ｉから選ばれるハロゲン原子を表す。)で表されるハロゲン化アルキルと、下記一般式（４）
Ｒ７ＯＭ２ （４）
（式中Ｒ７は炭化水素基を表し、炭素数１〜２０のアルキル基、フェニル基、ナフチル基から選ばれるいずれの基でもよい。Ｍ２はＬｉ、Ｎａ、Ｋの中から選ばれる金属原子を表す。）で表される金属アルコキシドを、溶媒の存在下に反応させ、下記一般式（５）
Ｒ６ＯＲ７ （５）
(式中Ｒ６、Ｒ７は前記と同じ意味を持つ。）で表されるエーテル化合物を製造することができる。
By using the magnetic fine particle-supported quaternary ammonium salt of the present invention represented by the above [Chemical Formula 5] as a catalyst, the following reaction can be performed.
That is, in the presence of the catalyst, the following general formula (3)
R 6 -X 2 (3)
(Wherein R 6 represents a hydrocarbon group, and may be any group selected from an alkyl group having 1 to 20 carbon atoms and a benzyl group. X 2 represents a halogen atom selected from F, Cl, Br, and I. And an alkyl halide represented by the following general formula (4)
R 7 OM 2 (4)
(Wherein R 7 represents a hydrocarbon group, and may be any group selected from an alkyl group having 1 to 20 carbon atoms, a phenyl group, and a naphthyl group. M 2 is a metal atom selected from Li, Na, and K. In the presence of a solvent, a metal alkoxide represented by the following general formula (5)
R 6 OR 7 (5)
(Wherein R 6 and R 7 have the same meaning as described above) can be produced.
この反応は、溶媒に原料物質、及び触媒を添加・溶解させる。溶媒には、水及び有機溶媒を用いる。有機溶媒は炭化水素、ハロゲン化炭化水素等を用いる。反応温度に制限はないが、低すぎると反応の進行が遅くなり、また、高すぎても望ましくない副反応が起こる可能性のあることから、２０℃〜１２０℃で行うのが好ましい。反応中は反応溶液を激しく撹拌する。反応終了後、反応容器の外壁に磁石を密着させることで、触媒のみが反応容器の内壁に集積する為、生成物を含む反応溶液のみをデカンテーションによって分別することが可能である。反応溶液をガスクロマトグラフィーにより分析することにより目的物質の収率を求めることができるが、溶媒抽出することによって目的物質を単離することも可能である。また、触媒は反応容器に残る為、次の反応にそのまま使用することができる。 In this reaction, a raw material and a catalyst are added and dissolved in a solvent. As the solvent, water and an organic solvent are used. As the organic solvent, hydrocarbon, halogenated hydrocarbon or the like is used. The reaction temperature is not limited, but if it is too low, the progress of the reaction is slow, and if it is too high, an undesirable side reaction may occur. During the reaction, the reaction solution is vigorously stirred. After the reaction is complete, the magnet is brought into close contact with the outer wall of the reaction vessel, so that only the catalyst accumulates on the inner wall of the reaction vessel, so that only the reaction solution containing the product can be separated by decantation. The yield of the target substance can be determined by analyzing the reaction solution by gas chromatography, but it is also possible to isolate the target substance by solvent extraction. Further, since the catalyst remains in the reaction vessel, it can be used as it is for the next reaction.
かくして、上記［化５］で表される本発明の磁性微粒子担持４級アンモニウム塩を相間移動触媒として用いることで効率的に相間移動反応を行うことができる。更に、磁気を利用することで、従来のポリマー担持型相間移動触媒に比べ、触媒の分離回収および再利用が大幅に簡便にすることが可能である。 Thus, the phase transfer reaction can be efficiently performed by using the magnetic fine particle-supported quaternary ammonium salt of the present invention represented by the above [Chemical Formula 5] as a phase transfer catalyst. Furthermore, by utilizing magnetism, it is possible to greatly simplify the separation and recovery and reuse of the catalyst as compared with the conventional polymer-supported phase transfer catalyst.
更に詳細な説明の為、以下に実施例を記述するが、本発明はこれらの実施例に限定されるものではない。
（実施例１）（マグネタイト微粒子の製造）
塩化鉄（II）４水和物１．９９ｇと塩化鉄（III）６水和物３．２４ｇを蒸留水２．４lに加え、減圧脱気し、窒素雰囲気下で撹拌した。均一溶液になるまで撹拌した後、１．５Ｎの水酸化アンモニウム水溶液を激しく撹拌しながら溶液のｐＨが約９になるまで滴下した。生成した黒色コロイドはネオジウム磁石により凝集させ、上澄み液はデカンテーションにより取り除いた。残った黒色沈殿を蒸留水で５回、エタノールで２回洗浄した後、減圧乾燥を行い１．６３ｇのマグネタイトを得た。
For further detailed description, examples will be described below, but the present invention is not limited to these examples.
(Example 1) (Production of magnetite fine particles)
1.99 g of iron (II) chloride tetrahydrate and 3.24 g of iron (III) chloride hexahydrate were added to 2.4 l of distilled water, degassed under reduced pressure, and stirred under a nitrogen atmosphere. After stirring until a homogeneous solution was obtained, 1.5N aqueous ammonium hydroxide solution was added dropwise with vigorous stirring until the pH of the solution reached about 9. The produced black colloid was aggregated with a neodymium magnet, and the supernatant was removed by decantation. The remaining black precipitate was washed 5 times with distilled water and twice with ethanol, and then dried under reduced pressure to obtain 1.63 g of magnetite.
（実施例２）（ヨウ化トリエチル［３−（トリメトキシシリル）プロピル］アンモニウムの製造）
（３−ヨードプロピル）トリメトキシシラン１．４５ｇをジクロロメタン５ｍｌに溶解し、トリエチルアミン０．５６ｇを加えて４０℃で２４時間撹拌した。混合物を減圧濃縮して得られた固体をヘキサン、エーテルでそれぞれ３回洗浄した後、減圧乾燥する事により、ヨウ化トリエチル［３−（トリメトキシシリル）プロピル］アンモニウム１．５５ｇを得た（収率７９％）。
１Ｈ−ＮＭＲ（４９９ＭＨｚ，ＣＤＣｌ３）：δ＝０．７４（ｔ，２Ｈ，Ｊ＝７．６Ｈｚ），１．４１（ｔ，９Ｈ，Ｊ＝７．３Ｈｚ），１．７５−１．８５（ｍ，２Ｈ），３．２９−３．３５（ｍ，２Ｈ），３．４８（ｑ，６Ｈ，Ｊ＝７．３Ｈｚ），３．５９（ｓ，９Ｈ）． １３Ｃ−ＮＭＲ（１２５ＭＨｚ，ＣＤＣｌ３）：δ＝５．４，８．１，１５．８，５０．７，５３．７，５８．８． ＦＡＢ−ＭＳ（ｐｏｓｉｔｉｖｅ）：ｍ／ｚ＝２６４（［Ｍ−Ｉ］）．
Example 2 (Production of triethyl [3- (trimethoxysilyl) propyl] ammonium iodide)
1.45 g of (3-iodopropyl) trimethoxysilane was dissolved in 5 ml of dichloromethane, 0.56 g of triethylamine was added, and the mixture was stirred at 40 ° C. for 24 hours. The solid obtained by concentrating the mixture under reduced pressure was washed three times with hexane and ether, respectively, and then dried under reduced pressure to obtain 1.55 g of triethyl [3- (trimethoxysilyl) propyl] ammonium iodide (yield). 79%).
1 H-NMR (499 MHz, CDCl 3 ): δ = 0.74 (t, 2H, J = 7.6 Hz), 1.41 (t, 9H, J = 7.3 Hz), 1.75-1.85 (M, 2H), 3.29-3.35 (m, 2H), 3.48 (q, 6H, J = 7.3 Hz), 3.59 (s, 9H). 13 C-NMR (125 MHz, CDCl 3 ): δ = 5.4, 8.1, 15.8, 50.7, 53.7, 58.8. FAB-MS (positive): m / z = 264 ([M-I]).
（実施例３）（ヨウ化トリ−ｎ−ブチル［３−（トリメトキシシリル）プロピル］アンモニウムの製造）
（３−ヨードプロピル）トリメトキシシラン５．８０ｇ、トリ−ｎ−ブチルアミン３．７１ｇ、トルエン１０ｍｌの混合物を１００℃で２４時間撹拌した。室温まで冷却後、分離した粗生成物を含む下層をヘキサン、エーテルでそれぞれ３回洗浄した後、減圧乾燥する事により、ヨウ化トリ−ｎ−ブチル［３−（トリメトキシシリル）プロピル］アンモニウム８．５０ｇを得た（収率８８％）。
１Ｈ−ＮＭＲ（４９９ＭＨｚ，ＣＤＣｌ３）：δ＝０．７６（ｔ，２Ｈ,Ｊ＝７．６Ｈｚ），０．９８（ｔ，９Ｈ，Ｊ＝７．３Ｈｚ），１．４１（ｓｅｘｔｅｔ，６Ｈ，Ｊ＝７．３Ｈｚ），１．６８−１．８６（ｍ，８Ｈ），３．３３−３．３９（ｍ，８Ｈ），３．５９（ｓ，９Ｈ）． １３Ｃ−ＮＭＲ（１２５ＭＨｚ，ＣＤＣｌ３）：δ＝５．５，１３．８，１６．３，１９．８，２４．３，５０．９，５９．３，６０．６． ＦＡＢ−ＭＳ（ｐｏｓｉｔｉｖｅ）：ｍ／ｚ＝３４８（［Ｍ-Ｉ］）．
Example 3 (Production of tri-n-butyl [3- (trimethoxysilyl) propyl] ammonium iodide)
A mixture of 5.80 g of (3-iodopropyl) trimethoxysilane, 3.71 g of tri-n-butylamine and 10 ml of toluene was stirred at 100 ° C. for 24 hours. After cooling to room temperature, the lower layer containing the separated crude product was washed three times with hexane and ether, and then dried under reduced pressure to give tri-n-butyl iodide [3- (trimethoxysilyl) propyl] ammonium iodide 8 .50 g was obtained (88% yield).
1 H-NMR (499 MHz, CDCl 3 ): δ = 0.76 (t, 2H, J = 7.6 Hz), 0.98 (t, 9H, J = 7.3 Hz), 1.41 (sextet, 6H , J = 7.3 Hz), 1.68-1.86 (m, 8H), 3.33-3.39 (m, 8H), 3.59 (s, 9H). 13 C-NMR (125 MHz, CDCl 3 ): δ = 5.5, 13.8, 16.3, 19.8, 24.3, 50.9, 59.3, 60.6. FAB-MS (positive): m / z = 348 ([M-I]).
（実施例４）（ヨウ化トリ−ｎ−ペンチル［３−（トリメトキシシリル）プロピル］アンモニウムの製造）
（３−ヨードプロピル）トリメトキシシラン５．８０ｇ、トリ−ｎ−ペンチルアミン４．５５ｇ、トルエン１０ｍｌの混合物を１２０℃で３６時間撹拌した。室温まで冷却後、混合物を減圧濃縮して得られる粗生成物をヘキサン／エーテル（１／１）、ヘキサンでそれぞれ３回洗浄した後、減圧乾燥する事により、ヨウ化トリ−ｎ−ペンチル［３−（トリメトキシシリル）プロピル］アンモニウム７．６４ｇを得た（収率７４％）。
１Ｈ−ＮＭＲ（４９９ＭＨｚ，ＣＤＣｌ３）：δ＝０．７６（ｔ，２Ｈ，Ｊ＝７．３Ｈｚ），０．９４（ｔ，９Ｈ，Ｊ＝７．３Ｈｚ），１．３６−１．４５（ｍ，１２Ｈ），１．６６−１．８４（ｍ，８Ｈ），３．３０−３．４１（ｍ，８Ｈ），３．５９（ｓ，９Ｈ）． １３Ｃ−ＮＭＲ（１２５ＭＨｚ，ＣＤＣｌ３）：δ＝５．５，１０．１，１６．３，２２．１，２２．３，２８．５，５０．９，５９．５，６０．６．ＦＡＢ−ＭＳ（ｐｏｓｉｔｉｖｅ）：ｍ／ｚ＝３９０（[Ｍ−Ｉ]）．
Example 4 (Production of tri-n-pentyl iodide [3- (trimethoxysilyl) propyl] ammonium iodide)
A mixture of 5.80 g of (3-iodopropyl) trimethoxysilane, 4.55 g of tri-n-pentylamine and 10 ml of toluene was stirred at 120 ° C. for 36 hours. After cooling to room temperature, the crude product obtained by concentrating the mixture under reduced pressure was washed three times with hexane / ether (1/1) and hexane, respectively, and then dried under reduced pressure to give tri-n-pentyl iodide [3 7.64 g of-(trimethoxysilyl) propyl] ammonium was obtained (yield 74%).
1 H-NMR (499 MHz, CDCl 3 ): δ = 0.76 (t, 2H, J = 7.3 Hz), 0.94 (t, 9H, J = 7.3 Hz), 1.36 to 1.45 (M, 12H), 1.66-1.84 (m, 8H), 3.30-3.41 (m, 8H), 3.59 (s, 9H). 13 C-NMR (125 MHz, CDCl 3 ): δ = 5.5, 10.1, 16.3, 22.1, 22.3, 28.5, 50.9, 59.5, 60.6. FAB-MS (positive): m / z = 390 ([M-I]).
（実施例５）（ヨウ化トリ−ｎ−ヘキシル［３−（トリメトキシシリル）プロピル］アンモニウムの製造）
実施例４においてトリ−ｎ−ペンチルアミンをトリ−ｎ−ヘキシルアミン５．３９ｇに変えた以外は実施例４と同様の操作を行い、ヨウ化トリ−ｎ−ヘキシル［３−（トリメトキシシリル）プロピル］アンモニウム１０．５ｇを得た（収率９４％）。
１Ｈ−ＮＭＲ（４９９ＭＨｚ，ＣＤＣｌ３）：δ＝０．７６（ｔ，２Ｈ，Ｊ＝７．６Ｈｚ），０．９０（ｔ，９Ｈ，Ｊ＝７．０Ｈｚ），１．２９−１．４７（ｍ，１８Ｈ），１．６５−１．８９（ｍ，８Ｈ），３．３０−３．４２（ｍ，８Ｈ），３．５９（ｓ，９Ｈ）． １３Ｃ−ＮＭＲ（１２５ＭＨｚ，ＣＤＣｌ３）：δ＝５．４，１３．７，１６．１，２２．１７，２２．２４，２５．９，３１．１，５０．７，５９．３，６０．４． ＦＡＢ−ＭＳ（ｐｏｓｉｔｉｖｅ）：ｍ／ｚ＝４３２（[Ｍ−Ｉ]）．
Example 5 (Production of tri-n-hexyl iodide [3- (trimethoxysilyl) propyl] ammonium iodide)
The same operation as in Example 4 was carried out except that tri-n-pentylamine was changed to 5.39 g of tri-n-hexylamine in Example 4, and tri-n-hexyl iodide [3- (trimethoxysilyl) iodide was used. Propyl] ammonium 10.5 g was obtained (yield 94%).
1 H-NMR (499 MHz, CDCl 3 ): δ = 0.76 (t, 2H, J = 7.6 Hz), 0.90 (t, 9H, J = 7.0 Hz), 1.29-1.47 (M, 18H), 1.65-1.89 (m, 8H), 3.30-3.42 (m, 8H), 3.59 (s, 9H). 13 C-NMR (125 MHz, CDCl 3 ): δ = 5.4, 13.7, 16.1, 22.17, 22.24, 25.9, 31.1, 50.7, 59.3, 60 .4. FAB-MS (positive): m / z = 432 ([M-I]).
（実施例６）（ヨウ化トリ−ｎ−ヘプチル［３−（トリメトキシシリル）プロピル］アンモニウムの製造）
実施例４においてトリ−ｎ−ペンチルアミンをトリ−ｎ−ヘプチルアミン６．２３ｇに変えた以外は実施例４と同様の操作を行い、ヨウ化トリ−ｎ−ヘプチル［３−（トリメトキシシリル）プロピル］アンモニウム１１．１ｇを得た（収率９２％）。
１Ｈ−ＮＭＲ（４９９ＭＨｚ，ＣＤＣｌ３）：δ＝０．７６（ｔ，２Ｈ，Ｊ＝７．６Ｈｚ），０．８９（ｔ，９Ｈ，Ｊ＝７．０Ｈｚ），１．２４−１．４４（ｍ，２４Ｈ），１．６５−１．８８（ｍ，８Ｈ），３．２９−３．４１（ｍ，８Ｈ），３．５９（ｓ，９Ｈ）． １３Ｃ−ＮＭＲ（１２５ＭＨｚ，ＣＤＣｌ３）：δ＝５．５，１３．９，１６．２，２２．３，２２．４，２６．７，２８．７，３１．５，５０．８，５９．４，６０．５． ＦＡＢ−ＭＳ（ｐｏｓｉｔｉｖｅ）：ｍ／ｚ＝４７４（[Ｍ-Ｉ]）．
Example 6 (Production of tri-n-heptyl [3- (trimethoxysilyl) propyl] ammonium iodide)
The same operation as in Example 4 was performed except that tri-n-pentylamine was changed to 6.23 g of tri-n-heptylamine in Example 4, and tri-n-heptyl iodide [3- (trimethoxysilyl) iodide was used. Propyl] ammonium 11.1 g was obtained (yield 92%).
1 H-NMR (499 MHz, CDCl 3 ): δ = 0.76 (t, 2H, J = 7.6 Hz), 0.89 (t, 9H, J = 7.0 Hz), 1.24-1.44 (M, 24H), 1.65-1.88 (m, 8H), 3.29-3.41 (m, 8H), 3.59 (s, 9H). 13 C-NMR (125 MHz, CDCl 3 ): δ = 5.5, 13.9, 16.2, 22.3, 22.4, 26.7, 28.7, 31.5, 50.8, 59 .4,60.5. FAB-MS (positive): m / z = 474 ([M-I]).
（実施例７）（ヨウ化トリ−ｎ−オクチル［３−（トリメトキシシリル）プロピル］アンモニウムの製造）
（３−ヨードプロピル）トリメトキシシラン４．６６ｇ、トリ−ｎ−オクチルアミン５．６９ｇ、トルエン５ｍｌの混合物を１２０℃で３６時間撹拌した。室温まで冷却後、混合物を減圧濃縮して得られる粗生成物をヘキサンで３回洗浄した後、エーテル２０ｍｌを加え撹拌した。不溶物をろ過により除いた後、ろ液を減圧濃縮する事により、ヨウ化トリ−ｎ−オクチル［３−（トリメトキシシリル）プロピル］アンモニウム６．６１ｇを得た（収率６４％）。
１Ｈ−ＮＭＲ（４９９ＭＨｚ，ＣＤＣｌ３）：δ＝０．７６（ｔ，２Ｈ，Ｊ＝７．６Ｈｚ），０．８８（ｔ，９Ｈ，Ｊ＝７．０Ｈｚ），１．２１−１．４５（ｍ，３０Ｈ），１．６４−１．８７（ｍ，８Ｈ），３．２７−３．４２（ｍ，８Ｈ），３．５９（ｓ，９Ｈ）． １３Ｃ−ＮＭＲ（１２５ＭＨｚ，ＣＤＣｌ３）：δ＝５．４，１４．０，１６．２，２２．４，２２．５，２６．４，２８．９８，２９．０，３１．６，５０．８，５９．４，６０．５． ＦＡＢ−ＭＳ（ｐｏｓｉｔｉｖｅ）：ｍ／ｚ＝５１６（[Ｍ-Ｉ]）．
Example 7 (Production of tri-n-octyl iodide [3- (trimethoxysilyl) propyl] ammonium iodide)
A mixture of 4.66 g of (3-iodopropyl) trimethoxysilane, 5.69 g of tri-n-octylamine and 5 ml of toluene was stirred at 120 ° C. for 36 hours. After cooling to room temperature, the crude product obtained by concentrating the mixture under reduced pressure was washed three times with hexane, and then 20 ml of ether was added and stirred. After removing insolubles by filtration, the filtrate was concentrated under reduced pressure to obtain 6.61 g of tri-n-octyl [3- (trimethoxysilyl) propyl] ammonium iodide (yield 64%).
1 H-NMR (499 MHz, CDCl 3 ): δ = 0.76 (t, 2H, J = 7.6 Hz), 0.88 (t, 9H, J = 7.0 Hz), 1.21-1.45 (M, 30H), 1.64-1.87 (m, 8H), 3.27-3.42 (m, 8H), 3.59 (s, 9H). 13 C-NMR (125 MHz, CDCl 3 ): δ = 5.4, 14.0, 16.2, 22.4, 22.5, 26.4, 28.98, 29.0, 31.6, 50 .8, 59.4, 60.5. FAB-MS (positive): m / z = 516 ([M-I]).
（実施例８）（触媒１の製造）
マグネタイト微粒子３０８ｍｇ、ヨウ化トリエチル［３−（トリメトキシシリル）プロピル］アンモニウム２．６０ｇ、クロロホルム１０ｍｌの混合物を室温で１分間超音波撹拌した後、更に１２時間還流撹拌した。室温まで冷却後、ネオジウム磁石を用いたマグネティックデカンテーションによって磁性体のみを分離し、クロロホルムで５回洗浄した。残った磁性微粒子を減圧乾燥する事により、３０３ｍｇの茶黒色微粒子を得た。得られた微粒子のハロゲン元素分析によりヨウ素の含有量は３．１８％であることがわかった。
(Example 8) (Production of catalyst 1)
A mixture of 308 mg of magnetite fine particles, 2.60 g of triethyl [3- (trimethoxysilyl) propyl] ammonium iodide, and 10 ml of chloroform was subjected to ultrasonic stirring for 1 minute at room temperature, and then further refluxed for 12 hours. After cooling to room temperature, only the magnetic material was separated by magnetic decantation using a neodymium magnet and washed 5 times with chloroform. The remaining magnetic fine particles were dried under reduced pressure to obtain 303 mg of brown black fine particles. The elemental content of the fine particles obtained was found to be 3.18% iodine.
（実施例９）（触媒２の製造）
マグネタイト微粒子５７８ｍｇ、ヨウ化トリ−ｎ−ブチル［３−（トリメトキシシリル）プロピル］アンモニウム５．９４ｇ、クロロホルム２０ｍｌの混合物を室温で１分間超音波撹拌した後、１２時間還流撹拌した。ネオジウム磁石を用いたマグネティックデカンテーションによって磁性体のみを分離し、クロロホルムで５回洗浄した。残った磁性微粒子を減圧乾燥する事により、５３１ｍｇの茶黒色微粒子を得た。得られた微粒子のハロゲン元素分析によりヨウ素の含有量は２．２９％であることがわかった。
(Example 9) (Production of catalyst 2)
A mixture of 578 mg of magnetite fine particles, 5.94 g of tri-n-butyl [3- (trimethoxysilyl) propyl] ammonium iodide, and 20 ml of chloroform was subjected to ultrasonic stirring for 1 minute at room temperature and then refluxed for 12 hours. Only the magnetic material was separated by magnetic decantation using a neodymium magnet and washed 5 times with chloroform. The remaining magnetic fine particles were dried under reduced pressure to obtain 531 mg of brown black fine particles. The elemental content of the fine particles obtained was found to have an iodine content of 2.29%.
（実施例１０）（触媒３の製造）
マグネタイト微粒子６６３ｍｇ、ヨウ化トリ−ｎ−ペンチル［３−（トリメトキシシリル）プロピル］アンモニウム７．４１g、クロロホルム２３ｍｌの混合物を室温で１分間超音波撹拌した後、１２時間還流撹拌した。ネオジウム磁石を用いたマグネティックデカンテーションによって磁性体のみを分離し、クロロホルムで５回洗浄した。残った磁性微粒子を減圧乾燥する事により、６２０ｍｇの茶黒色微粒子を得た。得られた微粒子のハロゲン元素分析によりヨウ素の含有量は１．６８％であることがわかった。
(Example 10) (Production of catalyst 3)
A mixture of 663 mg of magnetite fine particles, 7.41 g of tri-n-pentyl [3- (trimethoxysilyl) propyl] ammonium iodide and 23 ml of chloroform was subjected to ultrasonic stirring for 1 minute at room temperature and then refluxed for 12 hours. Only the magnetic material was separated by magnetic decantation using a neodymium magnet and washed 5 times with chloroform. The remaining magnetic fine particles were dried under reduced pressure to obtain 620 mg of brown black fine particles. The content of iodine was found to be 1.68% by halogen element analysis of the obtained fine particles.
（実施例１１）（触媒４の製造）
マグネタイト微粒子４９５ｍｇ、ヨウ化トリ−ｎ−ヘキシル［３−（トリメトキシシリル）プロピル］アンモニウム６．０１ｇ、クロロホルム１７ｍｌの混合物を室温で１分間超音波撹拌した後、１２時間還流撹拌した。ネオジウム磁石を用いたマグネティックデカンテーションによって磁性体のみを分離し、クロロホルムで５回洗浄した。残った磁性微粒子を減圧乾燥する事により、４７９ｍｇの茶黒色微粒子を得た。得られた微粒子のハロゲン元素分析によりヨウ素の含有量は１．４３％であることがわかった。
(Example 11) (Production of catalyst 4)
A mixture of 495 mg of magnetite fine particles, tri-n-hexyl iodide [3- (trimethoxysilyl) propyl] ammonium 6.01 g, and chloroform 17 ml was subjected to ultrasonic stirring for 1 minute at room temperature, and then refluxed for 12 hours. Only the magnetic material was separated by magnetic decantation using a neodymium magnet and washed 5 times with chloroform. The remaining magnetic fine particles were dried under reduced pressure to obtain 479 mg of brown black fine particles. The content of iodine was found to be 1.43% by halogen element analysis of the obtained fine particles.
（実施例１２）（触媒５の製造）
マグネタイト微粒子６１９ｍｇ、ヨウ化トリ−ｎ−ヘプチル［３−（トリメトキシシリル）プロピル］アンモニウム８．０５ｇ、クロロホルム２１ｍｌの混合物を室温で１分間超音波撹拌した後、１２時間還流撹拌した。ネオジウム磁石を用いたマグネティックデカンテーションによって磁性体のみを分離し、クロロホルムで５回洗浄した。残った磁性微粒子を減圧乾燥する事により、５６２ｍｇの茶黒色微粒子を得た。得られた微粒子のハロゲン元素分析によりヨウ素の含有量は１．５０％であることがわかった。
(Example 12) (Production of catalyst 5)
A mixture of 619 mg of magnetite fine particles, tri-n-heptyl [3- (trimethoxysilyl) propyl] ammonium iodide 8.05 g and chloroform 21 ml was subjected to ultrasonic stirring for 1 minute at room temperature and then refluxed for 12 hours. Only the magnetic material was separated by magnetic decantation using a neodymium magnet and washed 5 times with chloroform. The remaining magnetic fine particles were dried under reduced pressure to obtain 562 mg of brown black fine particles. The obtained fine particles were analyzed by halogen element analysis, and the iodine content was found to be 1.50%.
（実施例１３）（触媒６の製造）
マグネタイト微粒子４２９ｍｇ、ヨウ化トリ−ｎ−オクチル［３−（トリメトキシシリル）プロピル］アンモニウム５．９６g、クロロホルム１５ｍｌの混合物を室温で１分間超音波撹拌した後、１２時間還流撹拌した。ネオジウム磁石を用いたマグネティックデカンテーションによって磁性体のみを分離し、クロロホルムで５回洗浄した。残った磁性微粒子を減圧乾燥する事により、４０５ｍｇの茶黒色微粒子を得た。得られた微粒子のハロゲン元素分析によりヨウ素の含有量は１．２７％であることがわかった。
(Example 13) (Production of catalyst 6)
A mixture of 429 mg of magnetite fine particles, 5.96 g of tri-n-octyl [3- (trimethoxysilyl) propyl] ammonium iodide, and 15 ml of chloroform was subjected to ultrasonic stirring for 1 minute at room temperature and then refluxed for 12 hours. Only the magnetic material was separated by magnetic decantation using a neodymium magnet and washed 5 times with chloroform. The remaining magnetic fine particles were dried under reduced pressure to obtain 405 mg of brown black fine particles. The obtained fine particles were analyzed by halogen element analysis, and the iodine content was found to be 1.27%.
（実施例１４）
ナトリウムフェノキシド三水和物１２８ｍｇ(０．７５０ｍｍｏｌ)、触媒１(６４ｍｇ、アンモニウム塩０．０２２５ｍｍｏｌ相当)、１−ブロモブタン０．１２ｍｌ（１．５０ｍｍｏｌ）、トルエン１ｍｌ、水１ｍｌの混合物をオイルバス中１００℃で１２時間撹拌した。内標準物質としてテトラデカン２０μｌを反応混合物に加え、ガスクロマトグラフィーによりブチルフェニルエーテルの収率を求めた。その結果を表１に示す。
（実施例１４〜１９）
実施例１４において触媒１に代えて表１に示した触媒を用いた以外は実施例１４と同様の操作を行った。その結果を表１に示す。
(Example 14)
A mixture of 128 mg (0.750 mmol) of sodium phenoxide trihydrate, catalyst 1 (64 mg, corresponding to 0.0225 mmol of ammonium salt), 0.12 ml (1.50 mmol) of 1-bromobutane, 1 ml of toluene and 1 ml of water was placed in an oil bath. Stir at 12 ° C. for 12 hours. Tetradecane (20 μl) was added to the reaction mixture as an internal standard substance, and the yield of butylphenyl ether was determined by gas chromatography. The results are shown in Table 1.
(Examples 14 to 19)
The same operation as in Example 14 was carried out except that the catalyst shown in Table 1 was used in place of the catalyst 1 in Example 14. The results are shown in Table 1.
（比較例１）
実施例１４において触媒１を省略した以外は実施例１４と同様の操作を行った。その結果を表１に示す。
（比較例２）
実施例１４において触媒１に代えてヨウ化トリ−ｎ−ブチルアンモニウム８．３ｍｇ(０．０２２５ｍｍｏｌ)を用いた以外は実施例１４と同様の操作を行った。その結果を表１に示す。
(Comparative Example 1)
The same operation as in Example 14 was performed except that the catalyst 1 was omitted in Example 14. The results are shown in Table 1.
(Comparative Example 2)
The same operation as in Example 14 was carried out except that 8.3 mg (0.0225 mmol) of tri-n-butylammonium iodide was used in place of the catalyst 1 in Example 14. The results are shown in Table 1.
かかる表１の結果から明らかなように、触媒２、３、４はヨウ化トリ−ｎ−ブチルアンモニウム比べてほぼ同等或はそれ以上の触媒活性を有することが確認された。これにより本発明の磁性微粒子担持４級アンモニウム塩が相間移動反応に対して有効な触媒となることが認められたのである。 As is apparent from the results in Table 1, it was confirmed that the catalysts 2, 3, and 4 have substantially the same or higher catalytic activity than tri-n-butylammonium iodide. As a result, it was confirmed that the quaternary ammonium salt carrying the magnetic fine particles of the present invention is an effective catalyst for the phase transfer reaction.
（実施例２０〜２２）（触媒の再利用）
実施例１６の反応終了後、反応容器の外壁にネオジウム磁石を密着させることで触媒を反応容器の壁面に集めた。そのままデカンテーションすることで上澄み溶液のみを別の容器へと移した。反応容器に残った触媒をヘキサン、水でそれぞれ３回洗浄し、減圧乾燥した後、実施例１６と同じ条件下でのブチルフェニルエーテルの製造に用いた。これらの操作を繰り返し行った結果を表２に示す。
(Examples 20 to 22) (Reuse of catalyst)
After completion of the reaction in Example 16, the catalyst was collected on the wall of the reaction vessel by bringing a neodymium magnet into close contact with the outer wall of the reaction vessel. By decanting as it was, only the supernatant solution was transferred to another container. The catalyst remaining in the reaction vessel was washed three times with hexane and water, dried under reduced pressure, and then used for the production of butylphenyl ether under the same conditions as in Example 16. Table 2 shows the results of repeating these operations.
表２の結果から本発明の磁性微粒子担持相間移動触媒は磁気により迅速且つ容易に分離回収されるだけでなく、繰り返し再使用可能であることが確認された。 From the results in Table 2, it was confirmed that the phase transfer catalyst supporting magnetic fine particles of the present invention was not only rapidly and easily separated and recovered by magnetism, but could be reused repeatedly.
本発明の磁性微粒子担持４級アンモニウム塩は、磁気により迅速且つ容易に分離回収されるだけでなく、繰り返し再使用可能であることから、環境調和型の有機合成反応である相間移動反応において特に有用であり、多くの化合物の工業的製法に用いることができる。
The quaternary ammonium salt carrying the magnetic fine particles of the present invention is particularly useful in a phase transfer reaction, which is an environmentally friendly organic synthesis reaction, because it is not only quickly and easily separated and recovered by magnetism but also can be reused repeatedly. And can be used in the industrial production of many compounds.
Claims (4)
A phase transfer reaction using the magnetic fine particle-supported quaternary ammonium salt according to claim 1 as a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006131902A JP4586200B2 (en) | 2006-05-10 | 2006-05-10 | Quaternary ammonium salt supported on magnetic fine particles, production method thereof, magnetic fine particle-supported phase transfer catalyst comprising the same, and phase transfer reaction using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006131902A JP4586200B2 (en) | 2006-05-10 | 2006-05-10 | Quaternary ammonium salt supported on magnetic fine particles, production method thereof, magnetic fine particle-supported phase transfer catalyst comprising the same, and phase transfer reaction using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007301466A JP2007301466A (en) | 2007-11-22 |
| JP4586200B2 true JP4586200B2 (en) | 2010-11-24 |
Family
ID=38835869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006131902A Expired - Fee Related JP4586200B2 (en) | 2006-05-10 | 2006-05-10 | Quaternary ammonium salt supported on magnetic fine particles, production method thereof, magnetic fine particle-supported phase transfer catalyst comprising the same, and phase transfer reaction using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4586200B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4986117B2 (en) * | 2006-06-19 | 2012-07-25 | 独立行政法人産業技術総合研究所 | Phosphonium salt supported on magnetic fine particles, production method thereof, magnetic fine particle supported phase transfer catalyst comprising the phosphonium salt, and phase transfer reaction using the same |
| JP4984139B2 (en) * | 2007-05-29 | 2012-07-25 | 国立大学法人 岡山大学 | Method for producing catalyst cross-linking agent used for immobilization catalyst for synthesis of cyclic carbonate, method for producing immobilization catalyst, catalyst cross-linking agent used for immobilization catalyst, and immobilization catalyst |
| JP5704320B2 (en) * | 2010-03-04 | 2015-04-22 | 独立行政法人産業技術総合研究所 | Magnetic nanoparticles fixed osmium (VI) acid salt |
| CN107082870A (en) | 2012-03-30 | 2017-08-22 | 三菱化学株式会社 | Epoxy composite |
| KR101349713B1 (en) | 2012-06-25 | 2014-01-14 | 한국에너지기술연구원 | Method of harvesting microalgal biomass using amine-grafted magnetic nanoflocculant |
| KR102340560B1 (en) * | 2013-07-10 | 2021-12-21 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Continuous process for the preparation of thiocarboxylate silane |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59106493A (en) * | 1982-12-10 | 1984-06-20 | スチユワ−ト イ−・クレイン | Silyl quaternary ammonium compound and use |
| JPS60225648A (en) * | 1984-04-25 | 1985-11-09 | Toray Ind Inc | Fibrous phase-transfer catalyst |
| JPS615086A (en) * | 1984-06-18 | 1986-01-10 | Koshii Purezaabingu:Kk | Trialkyltrimethoxysilylpropylammonium halide and antifungal composition containing the same |
| JPH0564744A (en) * | 1991-09-06 | 1993-03-19 | Nok Corp | Production and recovery of hydrogenating catalyst |
| JPH06170245A (en) * | 1992-12-02 | 1994-06-21 | Tdk Corp | Method for recovering magnetic catalyst particle |
| JPH09169739A (en) * | 1995-12-19 | 1997-06-30 | Nippon Synthetic Chem Ind Co Ltd:The | Production of n-alkylformylimidazoles |
| JP2005060221A (en) * | 2003-07-31 | 2005-03-10 | Rikogaku Shinkokai | Composite material of organic substance and ferrite, and its production method |
-
2006
- 2006-05-10 JP JP2006131902A patent/JP4586200B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59106493A (en) * | 1982-12-10 | 1984-06-20 | スチユワ−ト イ−・クレイン | Silyl quaternary ammonium compound and use |
| JPS60225648A (en) * | 1984-04-25 | 1985-11-09 | Toray Ind Inc | Fibrous phase-transfer catalyst |
| JPS615086A (en) * | 1984-06-18 | 1986-01-10 | Koshii Purezaabingu:Kk | Trialkyltrimethoxysilylpropylammonium halide and antifungal composition containing the same |
| JPH0564744A (en) * | 1991-09-06 | 1993-03-19 | Nok Corp | Production and recovery of hydrogenating catalyst |
| JPH06170245A (en) * | 1992-12-02 | 1994-06-21 | Tdk Corp | Method for recovering magnetic catalyst particle |
| JPH09169739A (en) * | 1995-12-19 | 1997-06-30 | Nippon Synthetic Chem Ind Co Ltd:The | Production of n-alkylformylimidazoles |
| JP2005060221A (en) * | 2003-07-31 | 2005-03-10 | Rikogaku Shinkokai | Composite material of organic substance and ferrite, and its production method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007301466A (en) | 2007-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4586200B2 (en) | Quaternary ammonium salt supported on magnetic fine particles, production method thereof, magnetic fine particle-supported phase transfer catalyst comprising the same, and phase transfer reaction using the same | |
| Clark et al. | Catalysis of liquid phase organic reactions using chemically modified mesoporous inorganic solids | |
| Yang et al. | Highly stereoselective anti-Markovnikov hydrothiolation of alkynes and electron-deficient alkenes by a supported Cu-NHC complex | |
| US7375170B2 (en) | Organosilicon compound | |
| US7049266B2 (en) | Layered double hydroxides supported nanopalladium catalysts for Heck-, Suzuki, Sonogashira-, and Stille type coupling reactions of haloarenes | |
| CN105344378B (en) | It is a kind of for phosphotungstic acid metal organic framework of catalyzing cellulose hydrolysis and preparation method and application | |
| Dubey et al. | A biomimetic magnetically recoverable palladium nanocatalyst for the Suzuki cross-coupling reaction | |
| Didier et al. | Charge‐Transfer Interactions: An Efficient Tool for Recycling Bis (oxazoline)‐Copper Complexes in Asymmetric Henry Reactions | |
| Keller et al. | An efficient and recyclable dendritic catalyst able to dramatically decrease palladium leaching in Suzuki couplings | |
| Saha et al. | Heterogeneous catalysis over a barium carboxylate framework compound: Synthesis, X-ray crystal structure and aldol condensation reaction | |
| Michalek et al. | Synthesis of functional cobalt nanoparticles for catalytic applications. Use in asymmetric transfer hydrogenation of ketones | |
| Ma'mani et al. | Palladium catalyst supported on N-aminoguanidine functionalized magnetic graphene oxide as a robust water-tolerant and versatile nanocatalyst | |
| CN106582710A (en) | Method for preparing biphenyl by catalyzing Suzuki reaction through graphene-loaded palladium-copper nanocapsule | |
| Shakourian-Fard et al. | Synthesis of α-aminophosphonates in the presence of a magnetic recyclable Fe3O4@ SiO2-2mimSO3H nanocatalyst | |
| Hajipour et al. | Simultaneous immobilization of a matrix containing palladium and phase transfer catalyst on silica nanoparticles: application as a recoverable catalyst for the Heck reaction in neat water | |
| Samanta et al. | A mononuclear copper (II) complex immobilized in mesoporous silica: An efficient heterogeneous catalyst for the aerobic oxidation of benzylic alcohols | |
| US8557726B2 (en) | Chiral heterogeneous catalyst for assymmetric nitroaldol reaction | |
| Peng et al. | A highly efficient and recyclable catalyst—dendrimer supported chiral salen Mn (iii) complexes for asymmetric epoxidation | |
| US9376390B2 (en) | Methods of isolating (4-chloro-2-fluoro-3-substituted-phenyl)boronates and methods of using the same | |
| JP5704320B2 (en) | Magnetic nanoparticles fixed osmium (VI) acid salt | |
| JP4986117B2 (en) | Phosphonium salt supported on magnetic fine particles, production method thereof, magnetic fine particle supported phase transfer catalyst comprising the phosphonium salt, and phase transfer reaction using the same | |
| Hu et al. | MCM‐41‐Supported Bidentate Phosphine Rhodium Complex: An Efficient and Recyclable Heterogeneous Catalyst for the Hydrosilylation of Olefins | |
| Kutzscher et al. | Synthesis of the homochiral metal–organic framework DUT-129 based on a chiral dicarboxylate linker with 6 stereocenters | |
| CN106008401A (en) | Preparation method of N-formamide compound | |
| CN109746048B (en) | Multiphase rhodium-based hydroformylation catalyst, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080327 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100809 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100817 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100818 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130917 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130917 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |