JP4963033B2 - Method for producing 9,9-bis (aminoalkyl) fluorene compound - Google Patents
Method for producing 9,9-bis (aminoalkyl) fluorene compound Download PDFInfo
- Publication number
- JP4963033B2 JP4963033B2 JP2006079769A JP2006079769A JP4963033B2 JP 4963033 B2 JP4963033 B2 JP 4963033B2 JP 2006079769 A JP2006079769 A JP 2006079769A JP 2006079769 A JP2006079769 A JP 2006079769A JP 4963033 B2 JP4963033 B2 JP 4963033B2
- Authority
- JP
- Japan
- Prior art keywords
- bis
- fluorene
- fluorene compound
- aminoalkyl
- group
- 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
- -1 fluorene compound Chemical class 0.000 title claims description 23
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims description 23
- 125000004103 aminoalkyl group Chemical group 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 7
- COWHDUMHYFLLER-UHFFFAOYSA-N 3-[9-(2-cyanoethyl)fluoren-9-yl]propanenitrile Chemical compound C1=CC=C2C(CCC#N)(CCC#N)C3=CC=CC=C3C2=C1 COWHDUMHYFLLER-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- YREZIWUCYDRMPK-UHFFFAOYSA-N 3-[9-(3-aminopropyl)fluoren-9-yl]propan-1-amine Chemical compound C1=CC=C2C(CCCN)(CCCN)C3=CC=CC=C3C2=C1 YREZIWUCYDRMPK-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 125000002560 nitrile group Chemical group 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 0 **C1(*C#N)C(C=C*(*)C=C2)=C2C2=C1C=C*(*)C=C2 Chemical compound **C1(*C#N)C(C=C*(*)C=C2)=C2C2=C1C=C*(*)C=C2 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- RRUFLWHHNNUUCS-UHFFFAOYSA-N 2-[9-(cyanomethyl)fluoren-9-yl]acetonitrile Chemical compound C1=CC=C2C(CC#N)(CC#N)C3=CC=CC=C3C2=C1 RRUFLWHHNNUUCS-UHFFFAOYSA-N 0.000 description 1
- FPRMHGCEVRMZST-UHFFFAOYSA-N 2-[[9-(2-cyanobutyl)fluoren-9-yl]methyl]butanenitrile Chemical compound C(#N)C(CC1(C2=CC=CC=C2C=2C=CC=CC12)CC(CC)C#N)CC FPRMHGCEVRMZST-UHFFFAOYSA-N 0.000 description 1
- KRHHZQAGZNNUTL-UHFFFAOYSA-N 3-[2,7-dibromo-9-(2-cyanoethyl)fluoren-9-yl]propanenitrile Chemical compound C1=C(Br)C=C2C(CCC#N)(CCC#N)C3=CC(Br)=CC=C3C2=C1 KRHHZQAGZNNUTL-UHFFFAOYSA-N 0.000 description 1
- GDPAOCNTUZJTSL-UHFFFAOYSA-N 3-[2,7-dichloro-9-(2-cyanoethyl)fluoren-9-yl]propanenitrile Chemical compound ClC1=CC=2C(C3=CC(=CC=C3C2C=C1)Cl)(CCC#N)CCC#N GDPAOCNTUZJTSL-UHFFFAOYSA-N 0.000 description 1
- VWPBGFOHVFGIHJ-UHFFFAOYSA-N 3-[9-(2-cyanoethyl)-2,7-dimethoxyfluoren-9-yl]propanenitrile Chemical compound COC1=CC=2C(C3=CC(=CC=C3C2C=C1)OC)(CCC#N)CCC#N VWPBGFOHVFGIHJ-UHFFFAOYSA-N 0.000 description 1
- KBCZQMHUCPEILG-UHFFFAOYSA-N 3-[9-(2-cyanoethyl)-2,7-dimethylfluoren-9-yl]propanenitrile Chemical compound CC1=CC=2C(C3=CC(=CC=C3C2C=C1)C)(CCC#N)CCC#N KBCZQMHUCPEILG-UHFFFAOYSA-N 0.000 description 1
- RSGPPMADJNQSTM-UHFFFAOYSA-N 3-[9-(2-cyanopropyl)fluoren-9-yl]-2-methylpropanenitrile Chemical compound C(#N)C(CC1(C2=CC=CC=C2C=2C=CC=CC12)CC(C)C#N)C RSGPPMADJNQSTM-UHFFFAOYSA-N 0.000 description 1
- GYBJMSVRLMDMRU-UHFFFAOYSA-N 4-[9-(3-cyanobutyl)fluoren-9-yl]-2-methylbutanenitrile Chemical compound C(#N)C(CCC1(C2=CC=CC=C2C=2C=CC=CC12)CCC(C)C#N)C GYBJMSVRLMDMRU-UHFFFAOYSA-N 0.000 description 1
- YAJRMWHXSXNJKZ-UHFFFAOYSA-N 5-[9-(4-cyanobutyl)fluoren-9-yl]pentanenitrile Chemical compound C(#N)CCCCC1(C2=CC=CC=C2C=2C=CC=CC12)CCCCC#N YAJRMWHXSXNJKZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000005219 aminonitrile group Chemical group 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000743 hydrocarbylene group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、ポリアミドやポリイミドの原料として有用な９，９−ビス（アミノアルキル）フルオレン化合物の経済的な製造方法に関する。 The present invention relates to an economical method for producing a 9,9-bis (aminoalkyl) fluorene compound useful as a raw material for polyamide and polyimide.
９，９−ビス（アミノアルキル）フルオレン化合物は、自由体積を大きくするカルド骨格を有しており、特異な性質を有するポリアミドやポリイミドの原料として期待されている。従来、この９，９−ビス（アミノアルキル）フルオレン化合物の具体的な製造例としては、９，９−ビス（シアノエチル）フルオレンを、エタノール中、スポンジ（ラネー）ニッケル触媒の存在下で水素化して９，９−ビス（アミノプロピル）フルオレンを製造する方法が知られている（特許文献１）。この文献においては、目的物の収率や品質に関する記載はないが、蒸留精製した後も粘性ある液体として得られているところから、副生物である不純物をかなり含むものと考えられる。同じく９，９−ビス（シアノエチル）フルオレンを、アンモニアを含有するイソプロパノールやトルエン中、ケイ酸ナトリウムと酸化コバルトの混合物を水素還元することによって得られる触媒の存在下で水素化する方法も知られている（特許文献２、３）。この文献においては、目的物と共に、ニトリル基の一方のみが水素化されたアミノニトリルを含めた収率が記載されており、また反応時間が非常に長いところから、この方法では、短時間で二つのニトリル基を完全に水素化することは困難であると想定される。 The 9,9-bis (aminoalkyl) fluorene compound has a cardo skeleton that increases the free volume, and is expected as a raw material for polyamide and polyimide having unique properties. Conventionally, as a specific production example of the 9,9-bis (aminoalkyl) fluorene compound, 9,9-bis (cyanoethyl) fluorene is hydrogenated in ethanol in the presence of a sponge (Raney) nickel catalyst. A method for producing 9,9-bis (aminopropyl) fluorene is known (Patent Document 1). Although there is no description regarding the yield and quality of the target product in this document, it is considered that the product contains a substantial amount of impurities as a by-product because it is obtained as a viscous liquid after distillation purification. Also known is a method of hydrogenating 9,9-bis (cyanoethyl) fluorene in the presence of a catalyst obtained by hydrogen reduction of a mixture of sodium silicate and cobalt oxide in isopropanol or toluene containing ammonia. (Patent Documents 2 and 3). In this document, the yield including the target product and an aminonitrile in which only one of the nitrile groups is hydrogenated is described, and the reaction time is very long. It is assumed that it is difficult to completely hydrogenate two nitrile groups.
そこで本発明の目的は、９，９−ビス（シアノアルキル）フルオレン化合物を水素化することによって、相当する９，９−ビス（アミノアルキル）フルオレン化合物を、短時間の反応で収率よく製造する方法を提供することにある。 Accordingly, an object of the present invention is to produce a corresponding 9,9-bis (aminoalkyl) fluorene compound in a high yield with a short reaction time by hydrogenating the 9,9-bis (cyanoalkyl) fluorene compound. It is to provide a method.
すなわち本発明によれば、下記一般式（１）
本発明によれば、ポリアミド、ポリイミドの原料として有用な９，９−ビス（アミノアルキル）フルオレン化合物を、短時間で収率よく製造する方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing the 9,9-bis (aminoalkyl) fluorene compound useful as a raw material of polyamide and a polyimide with a sufficient yield in a short time can be provided.
上記一般式（１）で表される９，９−ビス（シアノアルキル）フルオレン化合物において、Ｒは炭素数１〜４のヒドロカルビレン基、例えばメチレン基、エチレン基、トリメチレン基、イソプロピリデン基、テトラメチレン基などであり、Ｘは、水素；ハロゲン、例えば、フッ素、塩素、臭素、沃素など；炭素数１〜４のアルキル基、例えば、メチル基、エチル基、イソプロピル基、ｓｅｃ−ブチル基、ｔ−ブチル基など；あるいは炭素数１〜３のアルコキシ基、例えば、メトキシ基、エトキシ基、プロポキシ基などを表し、二つのＸは同一でも、異なるものであってもよい。９，９−ビス（シアノアルキル）フルオレン化合物としてより具体的には、９，９−ビス（シアノメチル）フルオレン、９，９−ビス（２−シアノエチル）フルオレン、９，９−ビス（３−シアノプロピル）フルオレン、９，９−ビス（２−シアノプロピル）フルオレン、９，９−ビス（４−シアノブチル）フルオレン、９，９−ビス（３−シアノブチル）フルオレン、９，９−ビス（２−シアノブチル）フルオレン、２，７−ジクロロ−９，９−ビス（２−シアノエチル）フルオレン、２，７−ジブロモ−９，９−ビス（２−シアノエチル）フルオレン、２，７−ジメチル−９，９−ビス（２−シアノエチル）フルオレン、２，７−ジメトキシ−９，９−ビス（２−シアノエチル）フルオレンなどを代表例として例示することができる。 In the 9,9-bis (cyanoalkyl) fluorene compound represented by the general formula (1), R is a hydrocarbylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, an isopropylidene group, A tetramethylene group and the like, wherein X is hydrogen; halogen, for example, fluorine, chlorine, bromine, iodine, etc .; an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a t-butyl group or the like; or an alkoxy group having 1 to 3 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, or the like, and two Xs may be the same or different. More specific examples of the 9,9-bis (cyanoalkyl) fluorene compound include 9,9-bis (cyanomethyl) fluorene, 9,9-bis (2-cyanoethyl) fluorene, and 9,9-bis (3-cyanopropyl). ) Fluorene, 9,9-bis (2-cyanopropyl) fluorene, 9,9-bis (4-cyanobutyl) fluorene, 9,9-bis (3-cyanobutyl) fluorene, 9,9-bis (2-cyanobutyl) Fluorene, 2,7-dichloro-9,9-bis (2-cyanoethyl) fluorene, 2,7-dibromo-9,9-bis (2-cyanoethyl) fluorene, 2,7-dimethyl-9,9-bis ( 2-Cyanoethyl) fluorene, 2,7-dimethoxy-9,9-bis (2-cyanoethyl) fluorene and the like can be exemplified as representative examples.
本発明においては、上記９，９−ビス（シアノアルキル）フルオレン化合物を、アンモニアを含有するアルコール中、スポンジコバルト触媒の存在下で水素化して、相当する９，９−ビス（アミノアルキル）フルオレン化合物を製造するものである。溶媒として使用することができるアルコールとしては、メタノール、エタノール、イソプロパノール、ｎ−プロパノールなどを例示することができるが、メタノールが最も好ましい。好適なアルコールの使用量は、９，９−ビス（シアノアルキル）フルオレン化合物１質量部に対し、０．５〜２０質量部、好ましくは１〜１０質量部、とくに好ましくは２〜８質量部である。またアンモニアは、９，９−ビス（シアノアルキル）フルオレン化合物１モルに対して２〜２０モル、とくに２．５〜１０モルとなる割合で使用するのが好ましい。 In the present invention, the 9,9-bis (cyanoalkyl) fluorene compound is hydrogenated in an alcohol containing ammonia in the presence of a sponge cobalt catalyst to give a corresponding 9,9-bis (aminoalkyl) fluorene compound. Is to be manufactured. Examples of the alcohol that can be used as the solvent include methanol, ethanol, isopropanol, and n-propanol. Methanol is most preferable. The preferred amount of alcohol used is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, particularly preferably 2 to 8 parts by weight, based on 1 part by weight of the 9,9-bis (cyanoalkyl) fluorene compound. is there. Ammonia is preferably used in a proportion of 2 to 20 mol, particularly 2.5 to 10 mol, per mol of 9,9-bis (cyanoalkyl) fluorene compound.
本発明において触媒として使用されるスポンジコバルト触媒は、コバルトと、溶出される金属、例えばアルミニウム、珪素、亜鉛、錫等との合金から、侵食剤例えばアルカリ、酸などによって溶出される金属を溶出させて得られるスポンジ状形態の活性コバルトを主成分とする触媒である。スポンジコバルト触媒は、９，９−ビス（シアノアルキル）フルオレン化合物１質量部に対し、０．０１〜０．５質量部、好ましくは０．０５〜０．４質量部、とくに好ましくは０．１〜０．３質量部となる割合で使用するのが好ましい。 The sponge cobalt catalyst used as a catalyst in the present invention elutes metal eluted by an erodant such as an alkali or acid from an alloy of cobalt and an eluted metal such as aluminum, silicon, zinc or tin. The catalyst is mainly composed of sponge-like active cobalt. The sponge cobalt catalyst is 0.01 to 0.5 parts by weight, preferably 0.05 to 0.4 parts by weight, particularly preferably 0.1 to 1 part by weight of the 9,9-bis (cyanoalkyl) fluorene compound. It is preferable to use it at a ratio of ~ 0.3 parts by mass.
９，９−ビス（シアノアルキル）フルオレン化合物の水素化反応は、種々の方法によって行うことができる。例えば、耐圧反応釜に、アルコール、アンモニア、スポンジコバルト触媒及び９，９−ビス（シアノアルキル）フルオレン化合物を仕込み、所定温度まで昇温後、水素を導入することによって行うことができる。水素化は、通常、７０〜１５０℃、好ましくは９０〜１３０℃の温度で行われる。反応温度が低すぎると充分な反応速度を得ることができず、また反応温度が高くなり過ぎると、副反応や分解反応を伴いやすくなり、収率が低下する傾向が見られる。また反応圧力は、水素分圧で、通常、０．５〜３０ＭＰａ、好ましくは２〜２０ＭＰａである。反応時間は、触媒の使用量や反応温度、その他反応条件によっても異なるが、通常、０．５〜３０時間、工業的観点からは１〜２０時間の範囲であり、このような反応時間で反応が完結するように反応条件の設定をすることが好ましい。 The hydrogenation reaction of the 9,9-bis (cyanoalkyl) fluorene compound can be performed by various methods. For example, it can be carried out by charging alcohol, ammonia, a sponge cobalt catalyst and a 9,9-bis (cyanoalkyl) fluorene compound into a pressure-resistant reaction kettle, raising the temperature to a predetermined temperature, and then introducing hydrogen. The hydrogenation is usually performed at a temperature of 70 to 150 ° C, preferably 90 to 130 ° C. If the reaction temperature is too low, a sufficient reaction rate cannot be obtained, and if the reaction temperature is too high, side reactions and decomposition reactions tend to occur and the yield tends to decrease. The reaction pressure is a hydrogen partial pressure and is usually 0.5 to 30 MPa, preferably 2 to 20 MPa. The reaction time varies depending on the amount of catalyst used, the reaction temperature, and other reaction conditions, but is usually 0.5 to 30 hours, and 1 to 20 hours from an industrial point of view. It is preferable to set reaction conditions so that is completed.
反応終了後は、常法によって目的とする９，９−ビス（アミノアルキル）フルオレン化合物を単離することができる。例えば、反応液を冷却後、反応釜から取り出し、濾別によってスポンジコバルト触媒を除き、濾液を濃縮してアンモニアや溶媒のアルコールを回収すると共に、残渣として粗製の９，９−ビス（アミノアルキル）フルオレン化合物を単離することができる。必要に応じ、これを蒸留、晶析、再結晶などに付することによって精製することができる。 After completion of the reaction, the desired 9,9-bis (aminoalkyl) fluorene compound can be isolated by a conventional method. For example, after cooling the reaction solution, it is removed from the reaction kettle, the sponge cobalt catalyst is removed by filtration, the filtrate is concentrated to recover ammonia and alcohol as a solvent, and crude 9,9-bis (aminoalkyl) as a residue. Fluorene compounds can be isolated. If necessary, it can be purified by subjecting it to distillation, crystallization, recrystallization and the like.
以下、実施例により本発明をさらに詳細に説明する。尚、実施例及び比較例における分析は、下記条件の高速液体クロマトグラフィにより実施した。
測定条件
機器:日本分光８００
カラム：Ｉｎｅｒｔｓｉｌ ＯＤＳ−２ 長さ１５０ｍｍ、内径４．６ｍｍ
分析サンプル調製法：約５０ｍｇを５０ｍｌのジクロロメタンに溶解
注入量：５μＬ
溶離液：グラジエント分析
（メタノール１０％＋０．１％リン酸水溶液９０％）５分保持
１５分かけて
（メタノール４５％＋０．１％リン酸水溶液５５％）
１０分かけて
（メタノール８０％＋０．１％リン酸水溶液２０％）
流量：１ｍｌ／分
検出器：ＵＶ（２５４ｎｍ）
定量法：絶対検量線法
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the analysis in an Example and a comparative example was implemented by the high performance liquid chromatography of the following conditions.
Measurement conditions Equipment: JASCO 800
Column: Inertsil ODS-2 150 mm long, 4.6 mm inner diameter
Analytical sample preparation method: about 50 mg dissolved in 50 ml of dichloromethane Injection volume: 5 μL
Eluent: Gradient analysis
(Methanol 10% + 0.1% phosphoric acid aqueous solution 90%) Hold for 5 minutes
Take 15 minutes
(Methanol 45% + 0.1% phosphoric acid aqueous solution 55%)
Take 10 minutes
(Methanol 80% + 0.1% phosphoric acid aqueous solution 20%)
Flow rate: 1 ml / min Detector: UV (254 nm)
Quantitative method: Absolute calibration curve method
［実施例１］
１リットルのオートクレーブに、９，９−ビス（２−シアノエチル）フルオレン６９．５ｇ、スポンジコバルト触媒１４．１ｇ及び１４％アンモニア含有メタノール５１３．６ｇを仕込み（アンモニア／ニトリル（モル比）＝１６．６／１）、水素ガスで置換した後、１２０℃に昇温し、水素圧１１．０ＭＰａで、水素吸収が認められなくなるまで３．０時間保持した。その後反応液を冷却し、触媒を濾別した。エバポレーターにて濾液からメタノール及びアンモニアを留去し、粗製９，９−ビス（３−アミノプロピル）フルオレン８４．４ｇを得た。メタノールを除いて求めたガスクロマトグラフィ面積百分率法による純度は９８．７％であった。高速液体クロマトグラフィにより、９，９−ビス（３−アミノプロピル）フルオレン含量を求めて収率を算出したところ、９４．５モル％であった。
[Example 1]
A 1 liter autoclave was charged with 69.5 g of 9,9-bis (2-cyanoethyl) fluorene, 14.1 g of a sponge cobalt catalyst and 513.6 g of methanol containing 14% ammonia (ammonia / nitrile (molar ratio) = 16.6). / 1) After replacing with hydrogen gas, the temperature was raised to 120 ° C., and the hydrogen pressure was 11.0 MPa, and maintained for 3.0 hours until no hydrogen absorption was observed. Thereafter, the reaction solution was cooled, and the catalyst was filtered off. Methanol and ammonia were distilled off from the filtrate with an evaporator to obtain 84.4 g of crude 9,9-bis (3-aminopropyl) fluorene. The purity determined by gas chromatography area percentage method excluding methanol was 98.7%. When the 9,9-bis (3-aminopropyl) fluorene content was determined by high performance liquid chromatography and the yield was calculated, it was 94.5 mol%.
［比較例１］
０．５リットルのオートクレーブに、９，９−ビス（２−シアノエチル）フルオレン５．４ｇ、スポンジニッケル触媒４．５ｇ及びエタノール１１０．０ｇを仕込み、水素ガスで置換した後、１１０℃に昇温し、水素圧１１．０ＭＰａで、水素吸収が認められなくなるまで９．０時間保持した。その後反応液を冷却し、触媒を濾別した。エバポレーターにて濾液からエタノールを留去し、粗製９，９−ビス（３−アミノプロピル）フルオレンを得た。エタノールを除いて求めたガスクロマトグラフィ面積百分率法による純度は５３．８％であり、片方のニトリル基のみが水素化されたモノアミノモノニトリル体が１９．１％残存していた。
[Comparative Example 1]
In a 0.5 liter autoclave, 5.4 g of 9,9-bis (2-cyanoethyl) fluorene, 4.5 g of sponge nickel catalyst and 110.0 g of ethanol were charged, and replaced with hydrogen gas. At a hydrogen pressure of 11.0 MPa, the mixture was held for 9.0 hours until no hydrogen absorption was observed. Thereafter, the reaction solution was cooled, and the catalyst was filtered off. Ethanol was distilled off from the filtrate with an evaporator to obtain crude 9,9-bis (3-aminopropyl) fluorene. The purity determined by gas chromatography area percentage method excluding ethanol was 53.8%, and 19.1% of a monoaminomononitrile body in which only one nitrile group was hydrogenated remained.
［比較例２］
０．２リットルのオートクレーブに、９，９−ビス（２−シアノエチル）フルオレン５．０ｇ、スポンジニッケル触媒１．１ｇ及び１４％アンモニア含有メタノール５１．０ｇを仕込み、水素ガスで置換した後、７０℃に昇温し、水素圧１０．０ＭＰａで、水素吸収が認められなくなるまで４．０時間保持した。その後反応液を冷却し、触媒を濾別した。エバポレーターにて濾液からメタノール及びアンモニアを留去し、粗製９，９−ビス（３−アミノプロピル）フルオレンを得た。メタノールを除いて求めたガスクロマトグラフィ面積百分率法による純度は４３．１％であり、片方のニトリル基のみが水素化されたモノアミノモノニトリル体が４３．７％残存していた。
[Comparative Example 2]
A 0.2 liter autoclave was charged with 5.0 g of 9,9-bis (2-cyanoethyl) fluorene, 1.1 g of sponge nickel catalyst and 51.0 g of methanol containing 14% ammonia, and replaced with hydrogen gas. The hydrogen temperature was maintained at 4.0 MPa until the hydrogen absorption was not observed at a hydrogen pressure of 10.0 MPa. Thereafter, the reaction solution was cooled, and the catalyst was filtered off. Methanol and ammonia were distilled off from the filtrate with an evaporator to obtain crude 9,9-bis (3-aminopropyl) fluorene. The purity by gas chromatography area percentage method obtained by removing methanol was 43.1%, and 43.7% of a monoaminomononitrile body in which only one nitrile group was hydrogenated remained.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006079769A JP4963033B2 (en) | 2006-03-22 | 2006-03-22 | Method for producing 9,9-bis (aminoalkyl) fluorene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006079769A JP4963033B2 (en) | 2006-03-22 | 2006-03-22 | Method for producing 9,9-bis (aminoalkyl) fluorene compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007254337A JP2007254337A (en) | 2007-10-04 |
| JP4963033B2 true JP4963033B2 (en) | 2012-06-27 |
Family
ID=38628939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006079769A Expired - Fee Related JP4963033B2 (en) | 2006-03-22 | 2006-03-22 | Method for producing 9,9-bis (aminoalkyl) fluorene compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4963033B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5071923B2 (en) * | 2006-11-22 | 2012-11-14 | エア・ウォーター株式会社 | 9,9-bis (3-aminopropyl) -2,7-dimethoxyfluore |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2320029A (en) * | 1942-04-04 | 1943-05-25 | Resinous Prod & Chemical Co | 9, 9-di-(gamma-aminopropyl)-fluorene |
| US4007226A (en) * | 1970-07-29 | 1977-02-08 | Eastman Kodak Company | Nitrile hydrogenation process |
| US3728284A (en) * | 1970-07-29 | 1973-04-17 | Eastman Kodak Co | Nitrile hydrogenation catalyst |
| JP2713612B2 (en) * | 1989-08-24 | 1998-02-16 | 三井東圧化学株式会社 | Method for producing bis (aminomethyl) norcamphans |
| JPH08333308A (en) * | 1995-06-07 | 1996-12-17 | Koei Chem Co Ltd | Production of n,n'-bis(3-aminopropyl diaminoalkane |
| JP3937275B2 (en) * | 1999-03-08 | 2007-06-27 | 川研ファインケミカル株式会社 | Process for producing trifluoromethylbenzylamines |
| JP4535704B2 (en) * | 2003-09-22 | 2010-09-01 | 川研ファインケミカル株式会社 | Magnetized cobalt fluidized bed catalyst for hydrogenation reaction and method of using the catalyst |
| JP2007246439A (en) * | 2006-03-16 | 2007-09-27 | Air Water Inc | Method for producing 9,9-bis(aminoalkyl)fluorene compound |
| JP2007254336A (en) * | 2006-03-22 | 2007-10-04 | Air Water Inc | 9,9-bis(3-aminopropyl)-2,7-dihalofluorene |
-
2006
- 2006-03-22 JP JP2006079769A patent/JP4963033B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007254337A (en) | 2007-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2018505175A (en) | Method for producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine | |
| US20100068108A1 (en) | Coated reactors, production method thereof and use of same | |
| EP1873137B1 (en) | Production of Xylenediamines | |
| JP4963033B2 (en) | Method for producing 9,9-bis (aminoalkyl) fluorene compound | |
| US6881864B2 (en) | Production method of xylylenediamine | |
| US20110190541A1 (en) | Method for the synthesis of high purity primary diamines and/or triamines | |
| JP2008063335A (en) | Method for producing 1,2-diol from carbonyl compound | |
| JP3920524B2 (en) | Process for producing bistrifluoromethylbenzylamines | |
| JP4743960B2 (en) | Method for producing 3-amino-1-propanol | |
| US20070191639A1 (en) | Optically active 1-Aryl-2-fluoro-substituted ethylamine and method for producing same | |
| US20220064102A1 (en) | Process for preparation of highly pure fingolimod hydrochloride | |
| JP2007246439A (en) | Method for producing 9,9-bis(aminoalkyl)fluorene compound | |
| EP2279998B1 (en) | Synthesis of iodixanol in propyleneglycol | |
| EP2699538B1 (en) | Process for the preparation of alkyldiamines | |
| JP7140347B2 (en) | Method for producing 4-(piperidin-4-yl)morpholine | |
| JP4709352B2 (en) | Method for purifying 3-aminopropanol | |
| EP2277852B1 (en) | Synthesis of iodixanol in water | |
| EP2277854B1 (en) | Synthesis of iodixanol in 1-methoxy-2-propanol and water or methanol | |
| EP2251323A1 (en) | Method for the purification of entacapone | |
| US8962886B2 (en) | Synthesis of iodixanol in methanol | |
| CN116730848A (en) | Preparation method of 1, 3-bis [ (trimethylol) methylamino ] propane | |
| JPS63112562A (en) | Production of 5,6,7,8-tetrahydroquinolines | |
| JP4147809B2 (en) | Method for producing halogenated aromatic methylamines | |
| CA2710422C (en) | Synthesis of iodixanol in 1-methoxy-2-propanol and water or methanol | |
| US6960691B2 (en) | Production process for halogenated aromatic methylamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090120 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110928 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111011 |
|
| 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: 20120321 |
|
| 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: 20120321 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4963033 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150406 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 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |