JPH04501424A - N-fluoropyridinium pyridine heptafluorodiborate - Google Patents
N-fluoropyridinium pyridine heptafluorodiborateInfo
- Publication number
- JPH04501424A JPH04501424A JP2507555A JP50755590A JPH04501424A JP H04501424 A JPH04501424 A JP H04501424A JP 2507555 A JP2507555 A JP 2507555A JP 50755590 A JP50755590 A JP 50755590A JP H04501424 A JPH04501424 A JP H04501424A
- Authority
- JP
- Japan
- Prior art keywords
- pyridine
- water
- boron trifluoride
- fluorine
- fluoropyridinium
- 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.)
- Granted
Links
- PBJTXVTVKNXWHU-UHFFFAOYSA-N dioxidoboranyloxy(fluoro)borinate 1-fluoropyridin-1-ium pyridine Chemical compound C1=CC=NC=C1.[O-]B([O-])OB([O-])F.[O-]B([O-])OB([O-])F.[O-]B([O-])OB([O-])F.[O-]B([O-])OB([O-])F.[O-]B([O-])OB([O-])F.[O-]B([O-])OB([O-])F.[O-]B([O-])OB([O-])F.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1.F[N+]1=CC=CC=C1 PBJTXVTVKNXWHU-UHFFFAOYSA-N 0.000 title 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 229910052731 fluorine Inorganic materials 0.000 claims description 25
- 239000011737 fluorine Substances 0.000 claims description 25
- DKGVLWUCRGFFMN-UHFFFAOYSA-N pyridine;trifluoroborane Chemical compound FB(F)F.C1=CC=NC=C1 DKGVLWUCRGFFMN-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 23
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 20
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 238000007792 addition Methods 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- JTTWSWWMKSIJMC-UHFFFAOYSA-N 1-fluoropyridin-1-ium;pyridine Chemical compound C1=CC=NC=C1.F[N+]1=CC=CC=C1 JTTWSWWMKSIJMC-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000003682 fluorination reaction Methods 0.000 description 8
- 150000002894 organic compounds Chemical class 0.000 description 8
- -1 alcohol silyl ethers Chemical class 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- FJFYRFLASPYVTO-UHFFFAOYSA-N pyridine;dihydrofluoride Chemical compound F.F.C1=CC=NC=C1 FJFYRFLASPYVTO-UHFFFAOYSA-N 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- UWDCUCCPBLHLTI-UHFFFAOYSA-N 1-fluoropyridin-1-ium Chemical class F[N+]1=CC=CC=C1 UWDCUCCPBLHLTI-UHFFFAOYSA-N 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910015900 BF3 Inorganic materials 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000012025 fluorinating agent Substances 0.000 description 4
- 150000007824 aliphatic compounds Chemical class 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- JOTVUNWYAJBQFL-UHFFFAOYSA-M 1-fluoro-1-azoniabicyclo[2.2.2]octane;fluoride Chemical compound [F-].C1CC2CC[N+]1(F)CC2 JOTVUNWYAJBQFL-UHFFFAOYSA-M 0.000 description 2
- JFZMMCYRTJBQQI-UHFFFAOYSA-M 1-fluoropyridin-1-ium;trifluoromethanesulfonate Chemical compound F[N+]1=CC=CC=C1.[O-]S(=O)(=O)C(F)(F)F JFZMMCYRTJBQQI-UHFFFAOYSA-M 0.000 description 2
- BANWBNLRSDINSG-UHFFFAOYSA-N 1-fluoropyridin-2-one Chemical compound FN1C=CC=CC1=O BANWBNLRSDINSG-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- UIGGTEAYXRFRFL-UHFFFAOYSA-N pyridine trihydrofluoride Chemical compound F.F.F.N1=CC=CC=C1 UIGGTEAYXRFRFL-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- JIXDOBAQOWOUPA-UHFFFAOYSA-N 1-fluoro-2-methoxybenzene Chemical compound COC1=CC=CC=C1F JIXDOBAQOWOUPA-UHFFFAOYSA-N 0.000 description 1
- DJGHACRVDZEGJV-UHFFFAOYSA-N 3,5-dichloropyridine;trifluoroborane Chemical compound FB(F)F.ClC1=CN=CC(Cl)=C1 DJGHACRVDZEGJV-UHFFFAOYSA-N 0.000 description 1
- IIQFBBQJYPGOHJ-UHFFFAOYSA-N 4-(cyclohexen-1-yl)morpholine Chemical compound C1CCCC(N2CCOCC2)=C1 IIQFBBQJYPGOHJ-UHFFFAOYSA-N 0.000 description 1
- VAPOFMGACKUWCI-UHFFFAOYSA-N 4-(cyclopenten-1-yl)morpholine Chemical compound C1CCC=C1N1CCOCC1 VAPOFMGACKUWCI-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910017971 NH4BF4 Inorganic materials 0.000 description 1
- 241000287462 Phalacrocorax carbo Species 0.000 description 1
- 150000001260 acyclic compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- JHZPNBKZPAWCJD-UHFFFAOYSA-N ethyl 2-oxocyclopentane-1-carboxylate Chemical compound CCOC(=O)C1CCCC1=O JHZPNBKZPAWCJD-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- QROKOTBWFZITJZ-UHFFFAOYSA-N n-pyridin-2-ylacetamide Chemical compound CC(=O)NC1=CC=CC=N1 QROKOTBWFZITJZ-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 Ｎ−フルオロピリジニウムピリジンへブタフルオロシボレート本出願は１９８９ 年５月１２日に出願された出願番号第３５１，１１５号の一部継続出願である。[Detailed description of the invention] N-Fluoropyridinium pyridine to butafluorochemicals This application was filed in 1989. This is a partial continuation of Application No. 351,115 filed on May 12, 2015.
本発明はＮ−フルオロピリジニウムピリジンへブタフルオロシボレートに関する ものである。The present invention relates to butafluorochevate to N-fluoropyridinium pyridine. It is something.
多数のフッ素化試薬が当技術分野で知られている。ある種類のフッ素化試薬は電 子性フッ素化試薬として知られている。この種類のフッ素化試薬はＯ−Ｆまたは Ｎ−Ｆ結合を含む構造を特色とする。Ｎ−Ｆ結合を含む電子性フッ素化試薬には 下記のものが含まれる：１−フルオロ−・２−ピリドン、プリントン（Ｓ。A large number of fluorinating reagents are known in the art. Some types of fluorinating reagents It is known as a child fluorination reagent. This type of fluorinating reagent is O-F or It is characterized by a structure containing an N-F bond. For electronic fluorinated reagents containing N-F bonds, Includes: 1-Fluoro-2-pyridone, Purinton (S.
Ｔ、Ｐｕｒｒｉｎｇｔｏｎ）らにより教示、’ １−フルオロ−２−ピリドン： 有用なフッ素化試薬’ 、Ｊ、Ｏｒｇ、Ｃｈｅｍ、４８．７６１ （１９８３） ；Ｎ−フルオロ−Ｎ−アルキルスルホンアミド、バーネット（Ｗ、Ｅ、Ｂａｒｎ ｅｔｔｅ）により教示、′Ｎ−フルオローＮ−アルキルスルホンアミド：カルバ ニオンのフッ素化に有用な試薬’ 、Ｊ、Ａｍ、Ｃｈｅｍ、Ｓｏｃ、１０６．４ ５２ （１９８４）；Ｎ−フルオロキヌクリジニウムフルオリド、バンクス（Ｒ ，Ｅ、Ｂａｎｋｓ）らにより教示、′Ｎ−フルオロキヌクリジニウムフルオリド による電子性フッ素化’、Ｊ、ｏｆ Ｆｌｕｏｒｉｎｅ Ｃｈｅｍ、３２．４６ １ （１９８６）；ならびにＮ−フルオロピリジニウム塩、ウメモト（Ｔ、Ｕｍ ｅｍｏｔｏ）らにより教示、′Ｎ−フルオロピリジニウムトリフレートおよびそ の同族体、ビＮ−フルオロピリジニウム塩は各種有機化合物をフッ素化する能力 をもつ安定なフッ素化試薬であることが示されている。たとえばウメモト（Ｔ、 Ｕｍｅｍ。T., Purrington) et al. '1-Fluoro-2-pyridone: Useful Fluorinated Reagents', J. Org. Chem, 48.761 (1983) ; N-fluoro-N-alkylsulfonamide, Barnette (W, E, Barn 'N-Fluoro-N-alkylsulfonamide: carba Reagents useful for fluorination of ions', J, Am, Chem, Soc, 106.4 52 (1984); N-fluoroquinuclidinium fluoride, Banks (R 'N-fluoroquinuclidinium fluoride, taught by E. Banks et al. Electronic fluorination by 'J, of Fluorine Chem, 32.46 1 (1986); and N-fluoropyridinium salt, Umemoto (T, Um 'N-fluoropyridinium triflate and its A homologue of , the biN-fluoropyridinium salt has the ability to fluorinate various organic compounds. It has been shown to be a stable fluorinating reagent with a For example, Umemoto (T, Umem.
ｔｏ）ら、′Ｎ−フルオロピリジニウムトリフレートおよびその誘導体：有用な フッ素化試薬’、Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ ２７ （３７）、 ４４６５ （１９８６）には、これらの塩類が芳香族化合物をフッ素化し、およ び工ノールシリルエーテル類をα−フルオロケトンに転化するのに有用であると 報告されている。ウメモト（Ｔ、Ｕｍｅｍｏｔｏ）ら、′Ｎ−フルオロピリジニ ウム塩の塩基開始型反応；反応性種として報告される新規な環状カルベン′、工 且１ジンに転化することもできると報告されている。to) et al., 'N-fluoropyridinium triflate and its derivatives: useful Fluorinating Reagent’, Tetrahedron Letters 27 (37), 4465 (1986) that these salts fluorinate aromatic compounds and It is useful for converting alcohol silyl ethers into α-fluoroketones. It has been reported. Umemoto et al.'N-fluoropyridiny Base-initiated reaction of salts; novel cyclic carbenes reported as reactive species, It is also reported that it can be converted into 1 gin.
しかしＮ−フルオロピリジニウム塩はそれらの一般的製法が危険であるため不利 である。上記ウメモトらの最初の報文により教示されるように、フッ素をまず低 温でピリジンまたは置換ピリジンと反応させてビリジンジフルオリドを得る。However, N-fluoropyridinium salts are disadvantageous because their common manufacturing method is dangerous. It is. As taught by the original paper by Umemoto et al. mentioned above, fluorine is first reduced. Reaction with pyridine or substituted pyridine at room temperature gives pyridine difluoride.
第２工程でこのビリジンジフルオリドをＮ−フルオロピリジニウム塩に転化する 。In the second step, this pyridine difluoride is converted to N-fluoropyridinium salt. .
Ｎ−フルオロピリジニウムテトラフルオロポレートおよびその製法を下記に示す 欧州特許出願明細書２０４．５３５号明細書も参照されたい。当業者に知られて いるようにピリジンジフルオリドは本来不安定であり、０℃以下の温度ですら急 激に分解することが知られている。上記の製法を大規模に採用した場合、ビリジ ンジフルオリドの製造は一時的であっても極めて危険になるであろう。N-fluoropyridinium tetrafluoroporate and its production method are shown below. See also European Patent Application No. 204.535. known to those skilled in the art As shown in the figure, pyridine difluoride is inherently unstable, and even at temperatures below 0°C, it becomes unstable. It is known to decompose violently. If the above manufacturing method is adopted on a large scale, The production of difluoride, even temporarily, would be extremely dangerous.
上記の危険性に対応して、本発明者らはフッ素をピリジン−三フッ化ホウ素コン プレックスと反応させることにより、分離しうる量のピリジンジフルオリドの生 成なしにＮ−フルオロピリジニウムテトラフルオロボレートを製造することを試 みた。得られた生成物は全く予想外のものであった。In response to the above-mentioned risks, the present inventors replaced fluorine with pyridine-boron trifluoride compound. By reacting with Plex, a separable amount of pyridine difluoride can be produced. An attempt was made to produce N-fluoropyridinium tetrafluoroborate without saw. The product obtained was completely unexpected.
発明の要約 得られた生成物は下記の新規化合物である：この新規化合物はＮ−フルオロピリ ジニウムピリジンへブタフルオロシボレートと呼ばれるであろう。上記ウメモト らの最初の報文により教示されるＮ−フルオロピリジニウムテトラフルオロポレ ートと異なり、本発明化合物はさらに１個のピリジン環を含み、テトラフルオロ ボレート基ではな（ヘプタフルオロシボレート基を含む。またウメモトらはＮ− フルオロピリジニウムテトラフルオロポレートは９０−９１℃の融点をもつと報 告しているが、本発明の新規化合物は１９６−１９７℃の融点をもつ。Summary of the invention The product obtained is the following new compound: Zinium pyridine would be called butafluorochemical. Umemoto above N-fluoropyridinium tetrafluoropoles taught by the first paper of et al. Unlike the compound of the present invention, the compound of the present invention further contains one pyridine ring and has a tetrafluorocarbon ring. It is not a borate group (contains a heptafluorochevate group. Also, Umemoto et al. Fluoropyridinium tetrafluoroporate is reported to have a melting point of 90-91°C. However, the novel compounds of the present invention have a melting point of 196-197°C.
本発明化合物はフッ素化剤として有用であり、現在用いられているフッ素化側Ｎ −フルオロピリジニウムトリフレートより安価である。本発明化合物の他の利点 は、ピリジンジフルオリド中間体に伴う製造の危険性が排除され、本発明化合物 はより好都合な温度で製造しうろことである。The compounds of the present invention are useful as fluorinating agents, and currently used fluorinated N - Cheaper than fluoropyridinium triflate. Other advantages of the compounds of the invention eliminates the manufacturing risks associated with pyridine difluoride intermediates and makes the compounds of the invention is a scale produced at a more convenient temperature.
分離しうる量のピリジンジフルオリドの生成なしにＮ−フルオロピリジニウムテ トラフルオロボレート系塩を製造する本発明者らの試みに際して、本発明者らが フッ素を３，５−ジクロロピリジン−三フッ化ホウ素コンプレックスと反応させ た点を留意すべきである。上記ウメモトらの報文の教示に基づいて予想された前 記欧州特許出願明細書の例４５に示される３、５−ジクロロ−Ｎ−フルオロピリ ジニウムテトラフルオロポレート、本発明化合物の塩素化型などは生成しなかっ た。これはさらに本発明のＮ−フルオロピリジニウムピリジンへブタフルオロシ ボレートの意外性を証明する。N-fluoropyridinium difluoride without the formation of separable amounts of pyridine difluoride. In the present inventors' attempt to produce trafluoroborate salt, the present inventors Reacting fluorine with 3,5-dichloropyridine-boron trifluoride complex The following points should be kept in mind. As expected based on the teachings of the above paper by Umemoto et al. 3,5-dichloro-N-fluoropyrin as shown in Example 45 of the European Patent Application Specification Zinium tetrafluoroporate, chlorinated forms of the compounds of the present invention, etc. are not generated. Ta. This further converts the butafluorosil into the N-fluoropyridinium pyridine of the present invention. Proving the unexpectedness of borate.
本発明の他の利点は、以下の説明および特許請求の範囲の記載から明らかにな本 発明のＮ−フルオロピリジニウムピリジンへブタフルオロシボレートは、フッ素 を、溶剤に溶解したピリジン−三フッ化ホウ素と約−４０℃から約＋３５℃まで の温度で反応させることにより製造される。本発明化合物を製造するためには市 販のピリジン−三フッ化ホウ素を使用するか、またはピリジン−三フッ化ホウ素 は単にＢＦ３をピリジン上に導通することにより製造しつる。Other advantages of the invention will be apparent from the following description and claims. The inventive N-fluoropyridinium pyridine butafluorochevate is a fluorine with pyridine-boron trifluoride dissolved in a solvent from about -40°C to about +35°C. It is produced by reacting at a temperature of . In order to produce the compound of the present invention, Use commercially available pyridine-boron trifluoride or use pyridine-boron trifluoride. is prepared simply by passing BF3 over pyridine.
かなりの量のピリジン−三フッ化ホウ素を溶解し、フッ素に対して不活性であり 、かつ生成物に対して非反応性である溶剤がここでは有用である。有用な溶剤の 一例はアセトニトリルである。好ましくは溶剤は市販のアセトニトリルである。Dissolves significant amounts of pyridine-boron trifluoride and is inert to fluorine. Solvents that are , and non-reactive with the product are useful here. of useful solvents An example is acetonitrile. Preferably the solvent is commercially available acetonitrile.
好ましくは、溶解したピリジン−三フッ化ホウ素は約−２５℃から約＋２５℃ま で、より好ましくは約−５℃から約＋２５℃までの温度である。Preferably, the dissolved pyridine-boron trifluoride is heated from about -25°C to about +25°C. and more preferably at a temperature of about -5°C to about +25°C.
、次いで市販のフッ素を溶液に吹き込む。安全性の理由から、フッ素を市販の窒 素で希釈することが有利である。窒素の使用量に対して、フッ素の使用量は約５ −３５重量％、より好ましくは約１０−２０重量％である。一般に約１モル当量 のフッ素がアセトニトリル中のピリジン−三フッ化ホウ素に添加される。１モル 当量より多いフッ素の添加はフッ素を浪費し、一方１モル当量より少ないフッ素 の添加はピリジン−三フッ化ホウ素を浪費する。, then bubble commercially available fluorine into the solution. For safety reasons, fluorine should not be replaced with commercially available nitrogen. It is advantageous to dilute with pure water. The amount of fluorine used is approximately 5% compared to the amount of nitrogen used. -35% by weight, more preferably about 10-20% by weight. Generally about 1 molar equivalent of fluorine is added to pyridine-boron trifluoride in acetonitrile. 1 mole Adding more than an equivalent amount of fluorine wastes fluorine, while adding less than one molar equivalent of fluorine The addition of pyridine-boron trifluoride is wasted.
本発明の実施例１に報告するように、７ｇのピリジン−三フッ化ホウ素を５０ｍ Ｌのアセトニトリルに溶解し、そしてフッ素と反応させて、生成物収率６６％が 得られた。その際本発明者らは、スケールアップした場合これより多い量のピリ ジン−三フッ化ホウ素を用いると収率が低下することを見出した。As reported in Example 1 of the present invention, 7 g of pyridine-boron trifluoride was added to 50 m Dissolved in L of acetonitrile and reacted with fluorine, the product yield was 66%. Obtained. At that time, the present inventors believe that if scaled up, a larger amount of pyri It has been found that the yield decreases when using dine-boron trifluoride.
次いで本発明者らは、本発明の反応を水の存在下で行うことにより生成物収率が 予想外に改良されることを偶然に見出した。市販の溶剤は水を含有する可能性が あるので、溶剤は水の供給源として役立つであろう。たとえば市販のアセトニト リルの一試料は０．２２重量にの水、すなわち１． ＯＯＣＣのアセトニトリル 中に約１７０μｍの水を含有していた。市販のアセトニトリルの他の試料は０． ００５重量％、すなわち１００ｃｃのアセトニトリル中に約４μｌの水を含有し ていた。溶剤が不十分な量の水を含有するか、または水を含有しない場合は、下 記の通り要求される全量の水に達するために水を添加しなければならない。Next, the present inventors performed the reaction of the present invention in the presence of water to increase the product yield. I discovered by chance that it was an unexpected improvement. Commercially available solvents may contain water Since there is, the solvent will serve as a source of water. For example, commercially available acetonitol One sample of Lil contained 0.22 parts by weight of water, or 1. OOCC acetonitrile It contained approximately 170 μm of water. Other samples of commercially available acetonitrile have 0. 005% by weight, or approximately 4 μl of water in 100 cc of acetonitrile. was. If the solvent contains insufficient or no water, Water must be added to reach the total amount of water required as noted.
従って、好ましくはフッ素を水の存在下で、溶剤に溶解したピリジン−三フッ化 ホウ素と反応させる。好ましくは、存在する水の全量は出発ピリジン−三フッ化 ホウ素のｇ当たり約２−約１２μＩである。出発ピリジン−三フッ化ホウ素のｇ 当たり約２０μｌより多い水の使用はピリジンＢＦ４塩を沈殿させ、これは目的 生成物をもたらさず、かつ目的生成物を汚染させる。より好ましくは存在する水 の全量は出発ピリジン−三フッ化ホウ素のｇ当たり約３−約８μｍであり、極め て好ましくはｇ当たり約４−約６μｌである。Therefore, preferably fluorine is dissolved in a solvent with pyridine-trifluoride in the presence of water. React with boron. Preferably, the entire amount of water present is the starting pyridine-trifluoride. From about 2 to about 12 μI per gram of boron. g of starting pyridine-boron trifluoride The use of more than about 20 μl of water per water precipitates the pyridine BF4 salt, which is does not yield product and contaminates the desired product. More preferably water present The total amount of is about 3 to about 8 μm per gram of starting pyridine-boron trifluoride, and is extremely and preferably about 4 to about 6 μl per gram.
水は数種の異なる方法で反応混合物に添加することができる。たとえば溶剤に溶 解したピリジン−三フッ化ホウ素にフッ素との反応前に水を添加することができ る：この水の添加法はピリジンＢＦ４塩の沈殿が生じる可能性があるため望まし くない。他の例として、窒素流または空気流を水に吹き込み、ついでこの湿潤し たガスを反応器に導通して、定常的ではあるが極めて低速で水を連続供給するこ とができる；湿潤ガスの流量は、反応器中に出発ピリジン−三フッ化ホウ素に対 し要求される量の水を供給し、かつフッ素質量流量により指示される反応速度を 提供すべく調整される。他の好ましい方法においては、水を漸増添加し、水の漸 増添加速度はフッ素質量流量により決定される：このような漸増添加は連続的ま たは断続的に行うことができる。極めて好ましくは、各漸増添加量は出発ピリジ ン−三フッ化ホウ素のｇ当たり本釣０． ３−約２．０μｍである。Water can be added to the reaction mixture in several different ways. For example, Water can be added to the dissolved pyridine-boron trifluoride before the reaction with fluorine. : This water addition method is not desirable as it may cause precipitation of pyridine BF4 salt. Not. Another example is blowing a stream of nitrogen or air into the water and then Water is continuously supplied at a steady but extremely slow rate by passing the gas into the reactor. the flow rate of the humid gas is set relative to the starting pyridine-boron trifluoride in the reactor. supply the required amount of water and the reaction rate dictated by the fluorine mass flow rate. arranged to provide. In another preferred method, water is added in increments and the water is added in increments. The incremental addition rate is determined by the fluorine mass flow rate: such incremental additions can be continuous or It can be done intermittently or intermittently. Very preferably each incremental addition is equal to or less than the starting pyridine. 0.0% per gram of boron trifluoride. 3- Approximately 2.0 μm.
本発明者らは、アセトニトリル中においてＮ−フルオロピリジニウムピリジンへ ブタフルオロシボレート生成物がピリジン−三フッ化ホウ素より溶解性が低いこ とも見出した。ピリジン−三フッ化ホウ素対アセトニトリルの比率が大きすぎる 場合、生成物は溶液から排除され、フッ素の流れを妨害し、従って反応を妨害す る。好ましくはピリジン−三フッ化ホウ素ｇ対アセトニトリルＣＣの比率は０゜ ８を越えるべきでない。The present inventors converted N-fluoropyridinium pyridine in acetonitrile to The butafluorochevate product is less soluble than pyridine-boron trifluoride. I also found that Pyridine-boron trifluoride to acetonitrile ratio too high In the case of Ru. Preferably the ratio of pyridine-boron trifluoride g to acetonitrile CC is 0°. Should not exceed 8.
フッ素の取り込みは、反応器からの排出ガス流を水中のヨウ化カリウム溶液を入 れたバブラーに導通することにより簡便に探知することができる。フッ素の取り 込みが停止するとフッ素は反応器を通過し、直ちにバブラー内のヨウ化カリウム と反応してヨウ素を放出し、これがほとんど無色の溶液を暗褐色に変化させる。Fluorine uptake is achieved by introducing a solution of potassium iodide in water into the exhaust gas stream from the reactor. It can be easily detected by connecting it to a bubbler that has been removed. Fluoride removal When the loading stops, the fluorine passes through the reactor and immediately collects the potassium iodide in the bubbler. It reacts with iodine to release iodine, which turns the almost colorless solution dark brown.
Ｎ−フルオロピリジニウムピリジンへブタフルオロシボレートはフッ素化剤とし て有用である。この化合物は下記を含む有機化合物のフッ素化に有用である。N-Fluoropyridiniumpyridine to butafluorochrobate is used as a fluorinating agent. It is useful. This compound is useful in the fluorination of organic compounds including:
脂肪族化合物、たとえば１．−オクチルマグネシウムプロミドおよび二ル−ト誘 導体、たとえば３−ペンタノンエノールアセテート：非環式化合物、たとえば１ −モルホリノ−１−シクロヘキセン、１−モルホリノ−１−シクロペンテン、２ −カルボエトキシシクロペンタノンおよびシクロヘキサノントリメチルシリルエ ノールニー・チル：ならびに芳香族化合物、たとえばベンゼンおよびアニソール 。Aliphatic compounds, such as 1. -Octylmagnesium bromide and two-route derivatives Conductor, e.g. 3-pentanone enol acetate: Acyclic compound, e.g. 1 -morpholino-1-cyclohexene, 1-morpholino-1-cyclopentene, 2 -carboethoxycyclopentanone and cyclohexanone trimethylsilyl ether Norny chill: and aromatic compounds such as benzene and anisole .
フッ素化脂肪族化合物は薬剤を含めた多数の用途に有用であり、一方フッ素化芳 香族化合物は薬剤用および農業用化合物の中間体を含めた多数の用途に有用であ る。Fluorinated aliphatic compounds are useful in numerous applications, including pharmaceuticals, while fluorinated aromatic Aromatic compounds are useful in numerous applications, including as intermediates for pharmaceutical and agricultural compounds. Ru.
従って本発明は、Ｎ−フルオロピリジニウムピリジンへブタフルオロシボレート をフッ素化剤として用いることによる有機化合物のフッ素化法を提供する。本発 明による有機化合物のフッ素化法は、Ｎ−フルオロピリジニウムピリジンへブタ フルオロジポレー トを溶剤中の有機化合物と反応させることによる。好ましく は、溶剤は塩化メチレンまたはアセトニトリルである。Therefore, the present invention provides butafluorochemical conversion to N-fluoropyridinium pyridine. Provided is a method for fluorinating organic compounds by using as a fluorinating agent. Main departure A method of fluorination of organic compounds according to Akira et al. By reacting the fluorodiporate with an organic compound in a solvent. preferably The solvent is methylene chloride or acetonitrile.
本発明を以下の実施例によってより詳細に説明する。これらは本発明を限定する ものではない。The invention will be explained in more detail by the following examples. These limit the invention It's not a thing.
実施例１ 実施例１はＮ−フルオロピリジニウムピリジンへブタフルオロシボレートの製造 を目的とする。Example 1 Example 1 is the production of butafluorochrobate to N-fluoropyridinium pyridine. With the goal.
ピリジン−三フッ化ホウ素コンプレックス（７ｇ、０．０４７７ｍｏりを５０ｍ ｌ−のアセトニトリルに水浴温度で溶解した。窒素（６８ｅ ｅ／分）で希釈し たフッ素（８ｃ ｃ／分）を３時間吹き込んだ（０，０５４ｍｏ １のフッ素） 。添加終了後、溶液を四塩化炭素により摩砕処理し、冷却して５．２ｇの桃色固 体を得た。アセトンから再結晶して黄褐色結晶を得た。融点１９６−７℃。元素 分析・計算値（ＣＩＯＨＩＱＢ２Ｆ８Ｎ２） ： Ｃ，３６，２０；Ｈ，３，０ ４；Ｎ、８． ４４；実測値：Ｃ，３６，７５；Ｈ，３，３９；Ｎ、ｓ、０６． 分子量：ヨウ素滴定法による。計算値：３３１．６；実測値：３２３゜！’Ｆ ＮＭＲ： ＣＦ Ｃ１ｓから下流に４８．２ｐｐｍ （ＩＦ）およびＣＦＣｈか ら上流に１５０．ｌｐｐｍ （７Ｆ）： ’ＨＮＭＲ： ＣＨｓＣＮ： ９．２ ４ （ｄｄ、２Ｈ）、８．５ ８゜８ （ｍ、４Ｈ）、７．９−８．４ （ｍ、 ４Ｈ） ｐｐｍ；”Ｂ ＮＭＲ：ＮＨ４ＢＦ４に対して一、１２ｐｐｍ；”ＣＮ ＭＲ：１４８．８，１４８．０．１４２゜７．１３７．３，１３１．３および１ ２８．８ｐｐｍ。Pyridine-boron trifluoride complex (7g, 0.0477mol) in 50m 1- of acetonitrile at water bath temperature. Dilute with nitrogen (68e/min) Fluorine (8 c/min) was blown into the tank for 3 hours (0,054 mo1 fluorine). . After the addition was complete, the solution was triturated with carbon tetrachloride and cooled to give 5.2 g of a pink solid. I got a body. Recrystallization from acetone gave yellowish brown crystals. Melting point 196-7°C. element Analysis/calculation value (CIOHIQB2F8N2): C, 36, 20; H, 3, 0 4; N, 8. 44; Actual value: C, 36,75; H, 3,39; N, s, 06. Molecular weight: Based on iodine titration method. Calculated value: 331.6; Actual value: 323°! 'F NMR: 48.2 ppm downstream from CF C1s (IF) and CFCh 150. lppm (7F): 'HNMR: CHsCN: 9.2 4 (dd, 2H), 8.5 8゜8 (m, 4H), 7.9-8.4 (m, 4H) ppm;”B NMR: 1.12 ppm for NH4BF4;”CN MR: 148.8, 148.0.142゜7.137.3, 131.3 and 1 28.8ppm.
実施例２−９はＮ−フルオロピリジニウムピリジンへブタフルオロシボレートを フッ素化剤として用いることによる各種有機化合物のフッ素化を目的とする。Example 2-9 shows the addition of butafluorochevate to N-fluoropyridinium pyridine. The purpose is to fluorinate various organic compounds by using it as a fluorinating agent.
実施例２ 実施例１により得た試薬（０，２５ｇ）および２ｍＬのベンゼンを１５ｍＬの塩 化メチレン中で一晩還流した。フルオロベンゼンの存在はＧＣ−ＭＳによす指ア ニソール（０，１ｇ）および実施例１により得た試薬０．２５ｇをＣＨ２Ｃｌ２ 中で還流した。７時間後に、アニソールの２０％が２−フルオロ−および４−フ ルオロアニソールの１＝１混合物に転化された。２４時間の還流ののち、転化率 は７０％であった。Example 2 The reagent obtained in Example 1 (0.25 g) and 2 mL of benzene were mixed with 15 mL of salt. Refluxed in methylene chloride overnight. The presence of fluorobenzene was determined by GC-MS. Nisole (0.1 g) and 0.25 g of the reagent obtained from Example 1 were added to CH2Cl2 Reflux occurred inside. After 7 hours, 20% of the anisole has become 2-fluoro- and 4-fluoro- It was converted into a 1=1 mixture of fluoroanisole. After 24 hours of reflux, the conversion was 70%.
実施例４ ４０ｍＬの乾燥アセトニトリルに溶解した、実施例１により製造したフッ素化試 薬（９，９５ｇ、３０ｍｍｏ １）を、１５ｍＬの乾燥アセトニトリル中の１− モルホリノ−１−シクロヘキサン（３，３５ｇ、２０ｍｍｏｌ）の溶液に、３５ ℃以下の温度を維持する速度で徐々に添加した。次いで混合物を室温でさらに６ 時間撹拌した。２Ｎ ＨＣＩ （２５ｍＬ）水溶液を添加し、混合物を１時間還 流した。冷却した混合物を５０ｍＬの水で希釈し、３５ｍＬの塩化メチレンで３ 回抽出した。有機相を合わせて乾燥させ（ＭｇＳ０４）、溶剤を除去すると、３ −フルオロシクロヘキサノンを含有する残渣が残され、これをクロマトグラフィ ーにより精製した。Example 4 Fluorination test prepared according to Example 1 dissolved in 40 mL of dry acetonitrile The drug (9.95 g, 30 mmol 1) was dissolved in 1-1 in 15 mL dry acetonitrile. In a solution of morpholino-1-cyclohexane (3.35 g, 20 mmol), 35 The addition was done gradually at a rate that maintained the temperature below 0C. The mixture was then heated at room temperature for an additional 6 Stir for hours. 2N HCI (25 mL) aqueous solution was added and the mixture was refluxed for 1 hour. It flowed. The cooled mixture was diluted with 50 mL of water and diluted with 35 mL of methylene chloride. Extracted twice. The combined organic phases were dried (MgS04) and the solvent removed. - A residue containing fluorocyclohexanone is left, which is chromatographed. It was purified by
実施例５−９ 下記の有機化合物および実施例１により得た試薬０．２５ｇを塩化メチレン中で 還流して、フッ素化有機化合物を製造した。Example 5-9 The following organic compound and 0.25 g of the reagent obtained in Example 1 were dissolved in methylene chloride. Refluxing produced a fluorinated organic compound.
実施例 ５１−モルホリノ−１−シクロペンテン６２−カルボエトキシシクロペンタノン ７ シクロヘキサノントリメチルシリルエノールエーテル８３−ペンタノンエノ ールアセテート ９１−オクチルマグネシウムプロミド 実施例２−９は上記試薬が芳香族および脂肪族化合物をフッ素化することを示す 。Example 51-morpholino-1-cyclopentene 62-carboethoxycyclopentanone 7 Cyclohexanone trimethylsilyl enol ether 83-pentanone eno acetate 91-octylmagnesium bromide Examples 2-9 demonstrate that the above reagents fluorinate aromatic and aliphatic compounds. .
実施例１０ この例は本発明化合物中にＮ−フルオロピリジニウムカチオンが存在することに つき、さらに化学的証拠を提示する。Example 10 This example is based on the presence of an N-fluoropyridinium cation in the compound of the present invention. and provide further chemical evidence.
実施例１により得たフッ素化試薬（０，５ｇ）を、１ｇのＫＦを含有する５ｍＬ のアセトニトリル中で１時間還流した。反応混合物からピリジン、２−フルオロ ピリジンおよび２−アセトアミドピリジンの存在がＧＣ−ＭＳにより同定された 。後２者の生成物はウメモト（Ｔ、Ｕｍｅｍｏｔｏ）ら、′ＮＮ−フルオロビリ ラムの挙動と一致する。The fluorinating reagent (0.5 g) obtained in Example 1 was added to 5 mL containing 1 g of KF. of acetonitrile for 1 hour. Pyridine, 2-fluoro from the reaction mixture The presence of pyridine and 2-acetamidopyridine was identified by GC-MS. . The latter two products are described by Umemoto et al. Consistent with Ram's behavior.
比較例 この比較例は、スケールアップに際して生成物収率を高めるためにピリジン−三 フッ化ホウ素とフッ素の反応中に水を添加することの利点を示す。Comparative example This comparative example uses pyridine-3 to increase product yield during scale-up. The advantage of adding water during the reaction of boron fluoride and fluorine is shown.
反応器に８０．０ｇのピリジン−三フッ化ホウ素および３２０ｍＬのアセトニト リルを装填し、Ｎ２でパージした。反応器を水浴に装入し、撹拌された溶液中に Ｎ２中の１０％Ｆ２ （Ｖ／Ｖ）混合物を２００ｃｃ／分の速度で吹き込んだ。80.0 g of pyridine-boron trifluoride and 320 mL of acetonitol were added to the reactor. The rill was loaded and purged with N2. Place the reactor in a water bath and pour into the stirred solution. A 10% F2 in N2 (V/V) mixture was blown at a rate of 200 cc/min.
約３時間の添加ののち、反応により生じた廃ガスはヨウ化カリウムトラップを暗 色に変化させ、これは反応にＦ２が吸収されていないことを示した。反応器内容 物を冷却し、四塩化炭素を添加した：この添加により白色結晶が沈殿した（クロ ップ１）。これらの結晶を採取し、２５℃で数時間真空乾燥した（融点１９２− １９４℃）。ＩＨおよびＩ”Ｆ ＮＭＲは生成物の存在を示した。上記クロップ １からの濾液にさらに四塩化炭素を添加し、これにより第２クロツプ（クロップ ２）の結晶が沈殿した。これらの結晶を採取し、上記により乾燥させて融点１９ ４−１９７℃の固体を得た。この場合もＩＨおよび”Ｆ ＮＭＲは生成物の存在 を示した。クロップ１およびクロップ２の全収率は２４．９％であった。After approximately 3 hours of addition, the waste gas produced by the reaction passes through the potassium iodide trap in the dark. The color changed, indicating that no F2 was absorbed into the reaction. Reactor contents The material was cooled and carbon tetrachloride was added; this addition precipitated white crystals (chloro 1). These crystals were collected and vacuum dried at 25°C for several hours (melting point 192- 194℃). IH and I"F NMR showed the presence of product. Further carbon tetrachloride is added to the filtrate from 1, which produces a second crop. Crystals of 2) were precipitated. These crystals were collected and dried as described above to a melting point of 19 A solid was obtained at 4-197°C. In this case as well, IH and "F NMR indicate the presence of product. showed that. The overall yield of Crop 1 and Crop 2 was 24.9%.
実施例１１ 反応器に８０．０ｇのピリジン−三フッ化ホウ素コンプレックスおよび３００ｍ Ｌのアセトニトリルを装填し、Ｎ２でパージした。反応器を水浴に装入し、撹拌 された溶液中にＮ２中の１０％Ｆｚ（Ｖ／Ｖ）混合物を２００ｃｃ／分の速度で 吹き込んだ。２．５時間後に、反応により生じた廃ガスはヨウ化カリウム溶液を 暗色に変化させ、これはＦ２がもはや吸収されていないことを示した。次いで１ ００μｍの水を添加し、新たなヨウ化カリウムトラップを設置してフッ素化を再 開した。反応物はＦ２を１．５時間吸収し、この時点でトラップは暗色化した。Example 11 80.0 g of pyridine-boron trifluoride complex and 300 m Charged with L of acetonitrile and purged with N2. Place the reactor in a water bath and stir A 10% Fz (V/V) mixture in N2 was added to the solution at a rate of 200 cc/min. I blew it. After 2.5 hours, the waste gas produced by the reaction was poured into potassium iodide solution. It turned dark, indicating that F2 was no longer being absorbed. then 1 Add 00 μm water and install a new potassium iodide trap to restart fluorination. It opened. The reaction absorbed F2 for 1.5 hours, at which point the trap darkened.
反応物に５０μｌの水を添加し、フッ素化を再開した。１．５時間でＦ２はもは や吸収されなかった。さらに２回、各５０μｍの水を添加し、次いでその都度Ｆ ２を添加、吸収させた。反応液を冷却し、Ｒ−１１３を添加してほぼ白色の結晶 を沈殿させ、これを２５℃で数時間真空乾燥した。クロップ１については収量は ４７．３ｇ、すなわち５２．４％であり、融点は１９２−１９４℃であった。濾 液を同様に処理して第２クロツプの結晶を生成させ、これを濾過および真空乾燥 した。収量は２７．０ｇであり、融点は１５０−１８０℃であった。両クロップ においてＩＨおよびｌ’Ｆ ＮＭＲは生成物を立証した。クロップ２は若干の不 純物を示した。50 μl of water was added to the reaction and fluorination was restarted. F2 is no longer in 1.5 hours or not absorbed. Two more times, each time 50 μm of water was added, then F 2 was added and absorbed. The reaction solution was cooled and R-113 was added to form almost white crystals. was precipitated, and this was vacuum dried at 25° C. for several hours. For crop 1, the yield is 47.3 g, or 52.4%, and the melting point was 192-194°C. filter The liquid is treated similarly to produce a second crop of crystals, which is filtered and vacuum dried. did. The yield was 27.0 g, and the melting point was 150-180°C. both crops IH and I'F NMR confirmed the product. Crop 2 has some defects. Showed purity.
以上、本発明をその好ましい形態につき詳述したが、特許請求の範囲に定めた本 発明の範囲から逸脱することなく変更および修正をなしうることは明らかであろ う。The present invention has been described above in detail with respect to its preferred form, but the present invention as defined in the claims It will be clear that changes and modifications may be made without departing from the scope of the invention. cormorant.
手続補正書 １．事件の表示 ＰＣＴ／ＵＳ９０１０２３８４ ２、発明の名称 と− Ｎ−フルオロ去りジニウムピリジンへブタフルオロシボレート３、補正をする者 事件との関係 特許出願人 住 所 アメリカ合衆国ニューシャーシー州０７９６０゜モーリス・カウンティ 、モーリス・タウンシップ。Procedural amendment 1. Display of incidents PCT/US90102384 2. Name of the invention and- N-Fluoro leaving dinium pyridine to butafluorochemical converter 3, person making the correction Relationship to the incident: Patent applicant Address: Morris County, New Chassis, USA 07960 , Morris Township.
コロンビア・ロード・アンド−パーク・アベニュー（番地なし） 名 称 アライド−シグナル・インコーホレーテッド４、代理人 住 所 東京都千代田区大手町二丁目２番１号新大手町ビル ２０６区 電話３２７０−６６４１〜６６４６ １、明細書の［特許請求の範囲コを次の通り訂正します。Columbia Road and Park Avenue (no street address) Name: Allied-Signal Incorporated 4, Agent Address: Shin-Otemachi Building, 206-ku, 2-2-1 Otemachi, Chiyoda-ku, Tokyo Phone 3270-6641~6646 1. The claims in the specification are amended as follows.
「１１次式により表される化合物： 以上 国際調査報告 国際調査報告 ｕｓ ９００２３８４ ＳＡ ３７０３４"Compound represented by the 11th formula: that's all international search report international search report us 9002384 SA 37034
Claims (9)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US35111589A | 1989-05-12 | 1989-05-12 | |
| US351,115 | 1989-05-12 | ||
| US46065989A | 1989-09-13 | 1989-09-13 | |
| US460,659 | 1989-09-13 | ||
| PCT/US1990/002384 WO1990013541A1 (en) | 1989-05-12 | 1990-04-30 | N-fluoropyridinium pyridine heptafluorodiborate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04501424A true JPH04501424A (en) | 1992-03-12 |
| JPH0643401B2 JPH0643401B2 (en) | 1994-06-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2507555A Expired - Lifetime JPH0643401B2 (en) | 1989-05-12 | 1990-04-30 | N-fluoropyridinium pyridine heptafluorodiborate |
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| Country | Link |
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| JP (1) | JPH0643401B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07233097A (en) * | 1994-02-23 | 1995-09-05 | Chichibu Onoda Cement Corp | Method for producing electrophilic fluorinating agent |
-
1990
- 1990-04-30 JP JP2507555A patent/JPH0643401B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07233097A (en) * | 1994-02-23 | 1995-09-05 | Chichibu Onoda Cement Corp | Method for producing electrophilic fluorinating agent |
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| Publication number | Publication date |
|---|---|
| JPH0643401B2 (en) | 1994-06-08 |
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