JPS6021148B2 - New optically active pyridinium salt and method for producing the same - Google Patents
New optically active pyridinium salt and method for producing the sameInfo
- Publication number
- JPS6021148B2 JPS6021148B2 JP6042376A JP6042376A JPS6021148B2 JP S6021148 B2 JPS6021148 B2 JP S6021148B2 JP 6042376 A JP6042376 A JP 6042376A JP 6042376 A JP6042376 A JP 6042376A JP S6021148 B2 JPS6021148 B2 JP S6021148B2
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- formula
- ethyl
- tables
- optically active
- 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
Links
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 14
- -1 pyridone compound Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- FJBMSAMPYWVRAE-UHFFFAOYSA-N ethyl 2-ethyl-5-oxohex-2-enoate Chemical compound CCOC(=O)C(CC)=CCC(C)=O FJBMSAMPYWVRAE-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 3
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- GAPYHLNXLZTGEH-UHFFFAOYSA-N methyl 3-(4-methylpiperazin-1-yl)propanoate Chemical compound COC(=O)CCN1CCN(C)CC1 GAPYHLNXLZTGEH-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 235000010005 Catalpa ovata Nutrition 0.000 description 1
- 240000004528 Catalpa ovata Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000011914 asymmetric synthesis Methods 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SGGWFBYUWQRNRU-UHFFFAOYSA-N ethyl 2-ethyl-5-oxohex-3-enoate Chemical compound CCOC(=O)C(CC)C=CC(C)=O SGGWFBYUWQRNRU-UHFFFAOYSA-N 0.000 description 1
- SSJIXKNIALTVDP-UHFFFAOYSA-N ethyl 4-oxohex-2-enoate Chemical compound CCOC(=O)C=CC(=O)CC SSJIXKNIALTVDP-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は一般式
（式中、×はハロゲン原子を意味し、Ｒ１，Ｒ２および
Ｒ３は相互に同一か異って低級アルキル基を、Ｒ４はア
ルキル基またはシクロヘキシル基を意味する。Detailed Description of the Invention The present invention is based on the general formula (wherein x means a halogen atom, R1, R2 and R3 are the same or different from each other and represent a lower alkyl group, and R4 represents an alkyl group or a cyclohexyl group). means.
また＊は不整炭素原子を表わす。以下同様。）で示され
る光学的に活性な新規ピリジニウム塩およびその製造方
法に関するものである。Also, * represents an asymmetric carbon atom. Same below. ) and a method for producing the same.
本発明の新規ピリジニゥム塩（１）は後述するように光
学活性な化合物を得る為の試薬として有用である。本発
明の製造方法によれば新規ピリジニウム塩（１）は次式
で示される反応経路によって製造される。およびノ又は
すなわち一般式
で示され
る化合物を水酸化アンモニウムで処理して脱アシル化し
、一般式・よび／
又は
で・
示されるケトビニル化合物となし（第１工程）、次いで
化合物（ｍ）および／又は（ｍ′）に一般式（Ｗ）で示
される光学的活性アミン
を反応させ一般式
で示され
る新規なェナミン化合物となし（第２工程）、ついでこ
のものを水素化ナトリウムで処理することにより閉環さ
せ一般式で示さ
れる新規なピリドン化合物となし（第３工程）、ざらに
（Ｗ）をオキシ塩化リン及びホウフッ化物で処理するこ
と（第４工程）により合成される。The novel pyridinium salt (1) of the present invention is useful as a reagent for obtaining optically active compounds, as described below. According to the production method of the present invention, the novel pyridinium salt (1) is produced by the reaction route shown by the following formula. The compound represented by the general formula and/or is deacylated by treatment with ammonium hydroxide to form a ketovinyl compound represented by the general formula and/or (first step), and then the compound (m) and/or (m') is reacted with an optically active amine represented by the general formula (W) to form a new enamine compound represented by the general formula (second step), which is then treated with sodium hydride to form a ring-closing compound. A novel pyridone compound represented by the general formula is synthesized by treating pear (W) with phosphorus oxychloride and a borofluoride (fourth step).
本発明は目的化合物が新規であるばかりでなく、第２お
よび第３工程で得られる各中間化合物並びにそれ等を製
造する反応も新しいものである。以下本発明化合物（１
）の製造方法を工程順に説明する。In the present invention, not only the target compound is new, but also the intermediate compounds obtained in the second and third steps and the reactions for producing them are also new. The following compounds of the present invention (1
) will be explained step by step.
第１工程はＴｅｔｒａｈｅｄｒｏｎ，１２，６３−７５
（１９６１）に記載の方法に準じて実施できる。この工
程に於いて使用される前記一般式（０）で示される化合
物としてはＲＩおよびＲ２がメチル基、エチル基、プロ
ピル基およびブチル基である場合が挙げられる。第２工
程は化合物（ｍ）および／又は（ｍ′）に光学活性なア
ミン（Ｗ）を加え不活性溶媒の存在下に加熱還流させ、
その後共沸脱水することにより高収率で実施できる。光
学活性のアミンとしては例えば好ましくはｄ−または１
−Ｑ−シクロヘキシルェチルアミンが用いられる。この
工程の生成物は特に単離することなく、単に反応溶媒を
留去しただけで第３工程の出発物質とするのが操作上好
都合である。次に第３工程は化合物（Ｖ）に水素化ナト
リウムを加えベンゼン、トルェン、キシレン等の不活性
溶媒の存在下に加熱環流することによって行なわれる。The first step is Tetrahedron, 12, 63-75
(1961). Examples of the compound represented by the general formula (0) used in this step include cases where RI and R2 are a methyl group, an ethyl group, a propyl group, or a butyl group. In the second step, an optically active amine (W) is added to the compound (m) and/or (m') and heated to reflux in the presence of an inert solvent.
It can be carried out in high yield by subsequent azeotropic dehydration. Optically active amines include, for example, preferably d- or 1
-Q-cyclohexylethylamine is used. It is convenient for operation to use the product of this step as a starting material for the third step by simply distilling off the reaction solvent without isolating the product. Next, the third step is carried out by adding sodium hydride to compound (V) and heating to reflux in the presence of an inert solvent such as benzene, toluene, or xylene.
生成物の単離は反応後過剰の水素化ナトリウムを分解し
た後抽出操作により容易になされる。第４工程は化合物
（Ｗ）をまずオキシ塩化リンと共に加熱してクロル化し
、ついで反応液を濃縮した後無水溶媒に溶解しホウフッ
化物、例えばホウフツ化銀あるいはホウフツ化ナトリウ
ムを加えピリジニゥム塩を生成させることにより行なわ
れる。Isolation of the product is easily accomplished by extraction after decomposing excess sodium hydride after the reaction. In the fourth step, compound (W) is first heated with phosphorus oxychloride to chlorinate it, and then the reaction solution is concentrated, then dissolved in an anhydrous solvent, and a borofluoride, such as silver borofluoride or sodium borofluoride, is added to form a pyridinium salt. This is done by
生成した塩を単機するにはメチレンクロリド等の可溶溶
媒に溶解したピリジニウム塩の溶液を氷水で洗って残存
するリン酸等を除き、乾燥後濃縮し、エーテル等の不溶
溶媒を加えてピリジニウム塩の結晶を析出させることに
よって行なわれる。本発明の化合物は脂溶性が増大して
いる為に水のみならず各種有機溶媒に可溶であり、また
光学的活性を保持したまま反応に関与するため、これ等
の性質を利用してラセミ体を分割すること、および生理
活性物質例えば生理活性なアミノ酸の不斉合成を行なう
ことができる。To prepare a single unit of the generated salt, a solution of the pyridinium salt dissolved in a soluble solvent such as methylene chloride is washed with ice water to remove remaining phosphoric acid, dried and concentrated, and an insoluble solvent such as ether is added to prepare the pyridinium salt. This is done by precipitating crystals of Because the compounds of the present invention have increased fat solubility, they are soluble not only in water but also in various organic solvents, and because they participate in reactions while retaining optical activity, these properties can be used to create racemic Partitioning of the body and asymmetric synthesis of bioactive substances such as bioactive amino acids can be carried out.
以下実施例によって本発明をさらに詳細に説明する。The present invention will be explained in more detail below with reference to Examples.
参考例
−２ーヱチルー５ーオキソー３ーヘキセン酸エチルおよ
び２−エチル−５−オキソ−２−へキセン酸エチル一Ｑ
ーエチルーＱ−（３−オキソ−１ーブテニル）アセト酢
酸エチル４．５１２のこ塩化アンモニウム２．５６夕と
アンモニア水（濃度２８％）２．７２の‘を水１２の‘
に溶解した水溶液を内温４８一５０ご０に保ち、損梓下
５分間にわたり滴下する。Reference Example - Ethyl 2-ethyl-5-oxo-3-hexenoate and ethyl 2-ethyl-5-oxo-2-hexenoate-Q
-Ethyl-Q-(3-oxo-1-butenyl)ethyl acetoacetate 4.512 parts of ammonium chloride 2.56 parts of ammonia water (concentration 28%) 2.72 parts of water 12 parts of water
The aqueous solution dissolved in the solution was maintained at an internal temperature of 48-50 degrees Celsius, and was added dropwise over a period of 5 minutes.
滴下後、同温度で１５分間櫨梓を続けた後反応液を氷で
冷却し、次いでエーテルで抽出する。このェ−テル層を
水洗し、無水硫酸ナトリウム上で乾燥した後減圧蒸留し
て２−エチル一５−オキソ−３−へキセン酸エチルおよ
び２−エチル−５−オキソ−２ーヘキセン酸エチルの混
合物を得る。ｂｐ：８４一８７０（１側日夕）；収量：
２．６夕（収率７０．８％）実施例 １
−ｄ−Ｎ一（Ｑ一シクロヘキシルエチル）−３ーエチル
ー６ーメチルー２−ピリドン−参考例で得た２−エチル
−５ーオキソー３−へキセン酸エチルと２ーェチル−５
ーオキソー２ーヘキセン酸エチルの混合物９．４夕とｄ
−Ｑーシクロヘキシルェチルアミン（〔Ｑ〕容＝十３．
５６ｏ）６．４８夕とをトルェン５０の【に溶解し、２
０分間加熱還流した後共鍵脱水し、さらにトルェンを蟹
去する。After the dropwise addition, stirring was continued for 15 minutes at the same temperature, and the reaction solution was cooled with ice and then extracted with ether. This ether layer was washed with water, dried over anhydrous sodium sulfate, and then distilled under reduced pressure to obtain a mixture of ethyl 2-ethyl-5-oxo-3-hexenoate and ethyl 2-ethyl-5-oxo-2-hexenoate. get. bp: 84-870 (1st day and evening); Yield:
2.6 days (yield 70.8%) Example 1 -d-N-(Q-cyclohexylethyl)-3-ethyl-6-methyl-2-pyridone-2-ethyl-5-oxo-3-hexene obtained in Reference Example Ethyl acid and 2-ethyl-5
-Mixture of ethyl oxo-2-hexenoate 9.4 and d
-Q-cyclohexylethylamine ([Q] volume = 13.
56 o) Dissolve 6.48 mol and in 50 of toluene, 2
After heating under reflux for 0 minutes, the mixture was dehydrated and toluene was further removed.
油状物の残経を得るが、これは２エチル−５−（Ｑーシ
クロヘキシルエチルアミノ）一２．４−へキサジェン酸
エチルである。核磁気共鳴スペクトル〔ＣＤＣ１３，６
０ＭＨ２〕胸２．０２（３日，ｓ，ＣＨ３５．０８（Ｉ
Ｈ，ｄ，ＣＨ３
７．５０（ＩＨ，ｄ，
残澄を無水トルェン７０の‘に溶解し、水で冷却しつつ
油性水素化ナトリウム（含量５５％）２．２４夕を少量
ずつ加える。An oily residue is obtained, which is ethyl 2-ethyl-5-(Q-cyclohexylethylamino)-2,4-hexadienoate. Nuclear magnetic resonance spectrum [CDC13,6
0MH2] Chest 2.02 (3 days, s, CH35.08 (I
H, d, CH3 7.50 (IH, d, Dissolve the residue in 70 g of anhydrous toluene and add 2.24 g of oily sodium hydride (content 55%) little by little while cooling with water.
次いで１３５−１４０午０の油浴中で２時間還流を続け
た後反応液を少量ずつ氷水中に加え過剰の水素化ナトリ
ウムを分解し、濃塩酸でｐＨ１〜２となし、エーテルで
抽出する。エーテル層を重曹水および水で洗い、無水硫
酸ナトリウム上で乾燥した後減圧蒸留して目的物を得る
。ｂｐ：１３１−１３４ｏｏ（０．９側日夕）：収量：
９．１夕（収率７２．１％）〔Ｑ〕答＝十１０６０（Ｃ
＝３．８６：ＣＨ２ＣＩ２）元素分析値（Ｃ，ＢＨ２５
ＮＯとして）Ｃ（％） 日（％） Ｎ（％）
理論値 ７７．６８ １０．１９ ５．６６実験
値 ７７．３９ １０．４７ ５．３９実施例
２−１−Ｎ−（Ｑ一シクロヘキシルエチル）−３−エチ
ル一６ーメチルー２ーピリドンー１−Ｑーシクロヘキシ
ルェチルアミンから実施例１と同様にして１−Ｎ一（Ｑ
−シクロヘキシルエチル）一３−エチル一６ーメチルー
２ーピリドンを得る。After refluxing for 2 hours in an oil bath at 135-140 pm, the reaction solution was added little by little to ice water to decompose excess sodium hydride, adjusted to pH 1-2 with concentrated hydrochloric acid, and extracted with ether. The ether layer is washed with aqueous sodium bicarbonate and water, dried over anhydrous sodium sulfate, and then distilled under reduced pressure to obtain the desired product. bp: 131-134oo (0.9 side Sun/Sun): Yield:
9.1 night (yield 72.1%) [Q] Answer = 11060 (C
=3.86: CH2CI2) Elemental analysis value (C, BH25
(as NO) C (%) Day (%) N (%) Theoretical value 77.68 10.19 5.66 Experimental value 77.39 10.47 5.39 Example
From 2-1-N-(Q-cyclohexylethyl)-3-ethyl-6-methyl-2-pyridone-1-Q-cyclohexylethylamine, 1-N-(Q
-cyclohexylethyl)-13-ethyl-6-methyl-2-pyridone is obtained.
〔Ｑ〕答＝一９で（Ｃ＝０．６３；ＣＨ２ＣＩ２）実施
例 ３−ｄ一Ｎ一（Ｑ一シクロヘキシルエチル）一２ー
クロル−３ーエチルー６−メチルピリジニウムボロンテ
トラフルオライド−ｄ一Ｎ一（Ｑ−シクロヘキシルエチ
ル）−３−エチル−６−メチル−２ーピリドン１．０３
６夕をオキシ塩化リン３泌に溶解し、８０ｏｏで８時間
加熱擬梓する。[Q] Answer = 19 (C = 0.63; CH2CI2) Example 3-d1N1 (Q1cyclohexylethyl)12-chloro-3-ethyl-6-methylpyridinium borontetrafluoride-d1N1 (Q-cyclohexylethyl)-3-ethyl-6-methyl-2-pyridone 1.03
Dissolve 6 liters in phosphorus oxychloride and heat for 8 hours at 80°C.
反応液を濃縮後無水アセトン４Ｍに溶解‐し、この溶液
をホウフッ化銀１．７夕を無水アセトン４の【に溶かし
た溶液に滴下する。滴下後２時間縄梓を続ける。析出す
る沈澱を炉去し、炉液を濃縮して得た油状物を無水エー
テルでデカンテーションして洗いエーテルを留去する。
残澄を無水塩化メチレン２０私に溶解し、氷水５の【で
すばやく洗い、無水硫酸ナトリウム上で乾燥する。塩化
メチレン溶液を濃縮し、無水エーテルを加えると結晶が
析出する。これを炉取し、少量の無水塩化メチレンに溶
解し、無水エーテルを少量ずつ加えることにより再結晶
し、純粋な目的物を得る。ｍｐ：１３１℃；収量：０．
７８７夕（収率５３．１％）〔Ｑ〕容＝十３６．〆（Ｃ
＝７．１４：Ｃ比ＣＩ２）元素分析値（Ｃ，６日２５Ｎ
ＣＩＢＦ４として）Ｃ（％） 日（％） Ｎ（％）理論
値 ５４．３４ ７．１３ ３．９６実験値
５４．１５ ７．１６ ４．２５実施例 ４ーーー
Ｎ一（Ｑ一シクロヘキシルエチル）−２ークロルー３ー
エチルー６−メチルピリジニウムボロンテトラフルオラ
イド−１−Ｎ一（Ｑ−シクロヘキシルエチル）一３ーェ
チルー６ーメチルー２ーピリドンから実施例３と同様に
して１一Ｎ−（０−シクロヘキシルェチル）一２ークロ
ルー３ーエチルー６−メチルピリジニウムボロンテトラ
フルオライドを得る。After concentrating the reaction solution, it was dissolved in 4 M of anhydrous acetone, and this solution was added dropwise to a solution of 1.7 mol of silver borofluoride dissolved in 4 mol of anhydrous acetone. Continue rope azusa for 2 hours after instillation. The precipitate is removed from the oven, and the oil obtained by concentrating the solution from the oven is decanted with anhydrous ether, and the washed ether is distilled off.
Dissolve the residue in 20 parts of anhydrous methylene chloride, wash quickly with 5 parts of ice water, and dry over anhydrous sodium sulfate. When the methylene chloride solution is concentrated and anhydrous ether is added, crystals are precipitated. This is collected in an oven, dissolved in a small amount of anhydrous methylene chloride, and recrystallized by adding anhydrous ether little by little to obtain the pure target product. mp: 131°C; Yield: 0.
787 minutes (yield 53.1%) [Q] Volume = 136. 〆(C
=7.14:C ratio CI2) Elemental analysis value (C, 6 days 25N
As CIBF4) C (%) Day (%) N (%) Theoretical value 54.34 7.13 3.96 Experimental value
54.15 7.16 4.25 Example 4--N-(Q-cyclohexylethyl)-2-chloro-3-ethyl-6-methylpyridinium boron tetrafluoride-1-N-(Q-cyclohexylethyl)-3-ethyl-6-methyl- 11N-(0-cyclohexylethyl)12-chloro-3-ethyl-6-methylpyridinium boron tetrafluoride is obtained from 2-pyridone in the same manner as in Example 3.
Claims (1)
よびＲ＾３は相互に同一か異なつて低級アルキル基を、
Ｒ＾４はアルキル基またはシクロヘキシル基を意味する
。 また＊は不整炭素原子を表わす。）で示される光学的活
性なピリジニウム塩。２ ｄまたはｌ−Ｎ−（α−シク
ロヘキシルエチル）−２−クロル−３−エチル−６−メ
チルピリジニウムボロンテトラフルオライドである特許
請求の範囲第１項記載の化合物。 ３ 一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＾１，Ｒ＾２およびＲ＾３は相互に同一か異
なつて低級アルキル基を、Ｒ＾４はアルキル基またはシ
クロヘキシル基を意味する。 また＊は不整炭素原子を表わす。）で示されるピリドン
化合物にオキシ塩化リンおよびホウフツ化物を反応させ
ることを特徴とする一般式▲数式、化学式、表等があり
ます▼ （式中、Ｘはクロル原子を意味し、Ｒ＾１〜Ｒ
＾４および＊は前記の意味を有する。 ）で示される光学的活性なピリジニウム塩の製造方法。 ４ ピリドン化合物としてｄまたはｌ−Ｎ−（α−シク
ロヘキシルエチル）−３−エチル−６−メチル−２−ピ
リドンを使用する特許請求の範囲第３項記載の製造方法
。 ５ 一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＾１，Ｒ＾２およびＲ＾３は相互に同一か
異なつて低級アルキル基を、Ｒ＾４はアルキル基または
シクロヘキシル基を意味する。 また＊は不整炭素原子を表わす。）で示されるエナミン
化合物を水素化ナトリウムと反応させ一般式▲数式、化
学式、表等があります▼ （式中、Ｒ＾１〜Ｒ＾４および＊は前記の意味を表わ
す。 ）で示されるピリドン化合物となし、ついでこの化合物
にオキシ塩化リンおよびホウフツ化物を反応させること
を特徴とする一般式▲数式、化学式、表等があります▼ （式中、Ｘはクロル原子を意味し、Ｒ＾１〜Ｒ＾４お
よび＊は前記の意味を表わす。 ）で示される光学的活性なピリジニウム塩の製造方法。 ６ エナミン化合物としてｄ−またはｌ−２−エチル−
５−（α−シクロヘキシルエチルアミノ）−２，４−ヘ
キサジエン酸エチルを使用する特許請求の範囲第５項記
載の製造方法。 ７ 一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＾１およびＲ＾２は相互に同一か異なつて
、低級アルキル基を表わす。 ）で示されるケトビニル化合物と一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＾３は低級アルキル基を、Ｒ＾４はアルキ
ル基またはシクロヘキシル基を意味する。 また＊は不整炭素原子を表わす。）で示される光学活性
アミンを反応させて一般式▲数式、化学式、表等があり
ます▼ （式中、Ｒ＾１〜Ｒ＾４および＊は前記の意味
を有する。 ）で示されるエナミン化合物となし、ついでこれに水素
化ナトリウムを反応させ一般式▲数式、化学式、表等が
あります▼ （式中、Ｒ＾１〜Ｒ＾４および＊は前記の意味を有す
る。 ）で示されるピリドン化合物を得、これをオキシ塩化リ
ンおよびホウフツ化物を反応させることを特徴とする一
般式▲数式、化学式、表等があります▼ （式中、Ｘはクロル原子を意味し、Ｒ＾１〜Ｒ＾４お
よび＊は前記の意味を有する。 ）で示される光学的活性なピリジニウム塩の製造方法。 ８ ケトビニル化合物として２−エチル−５−オキソ−
３−ヘキセン酸エチルおよび／又は２−エチル−５−オ
キソ−２−ヘキセン酸エチル、光学活性アミンとしてｄ
−またはｌ−α−シクロヘキシルエチルアミンを使用す
る特許請求の範囲第７項記載の製造方法。[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, an alkyl group,
R^4 means an alkyl group or a cyclohexyl group. Also, * represents an asymmetric carbon atom. ) Optically active pyridinium salt. 2. The compound according to claim 1, which is 2d or l-N-(α-cyclohexylethyl)-2-chloro-3-ethyl-6-methylpyridinium borontetrafluoride. 3 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1, R^2 and R^3 are the same or different and represent a lower alkyl group, and R^4 represents an alkyl group or a cyclohexyl group. In addition, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting a pyridone compound represented by means a chlorine atom, and R^1~R
^4 and * have the meanings given above. ) A method for producing an optically active pyridinium salt. 4. The manufacturing method according to claim 3, wherein d or l-N-(α-cyclohexylethyl)-3-ethyl-6-methyl-2-pyridone is used as the pyridone compound. 5 General formulas ▲ Numerical formulas, chemical formulas, tables, etc. In addition, the enamine compound represented by * represents an asymmetric carbon atom is reacted with sodium hydride to form the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 to R^4 and * represents the above-mentioned meaning.) There are general formulas, mathematical formulas, chemical formulas, tables, etc., which are characterized by forming a pyridone compound represented by () and then reacting this compound with phosphorus oxychloride and a borofluoride. X means a chlorine atom, and R^1 to R^4 and * represent the above meanings.) A method for producing an optically active pyridinium salt. 6 d- or l-2-ethyl- as an enamine compound
The manufacturing method according to claim 5, which uses ethyl 5-(α-cyclohexylethylamino)-2,4-hexadienoate. 7 Ketovinyl compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are the same or different and represent lower alkyl groups.) There are chemical formulas, tables, etc. ▼ (In the formula, R^3 means a lower alkyl group, R^4 means an alkyl group or a cyclohexyl group, and * represents an asymmetric carbon atom.) The reaction produces an enamine compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. is reacted to obtain a pyridone compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting borofluorides ▼ (In the formula, X means a chloro atom, and R^1 to R^4 and * have the above meanings. ) A method for producing an optically active pyridinium salt. 8 2-ethyl-5-oxo- as a ketovinyl compound
Ethyl 3-hexenoate and/or ethyl 2-ethyl-5-oxo-2-hexenoate, d as optically active amine
- or l-α-cyclohexylethylamine is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6042376A JPS6021148B2 (en) | 1976-05-25 | 1976-05-25 | New optically active pyridinium salt and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6042376A JPS6021148B2 (en) | 1976-05-25 | 1976-05-25 | New optically active pyridinium salt and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52144673A JPS52144673A (en) | 1977-12-02 |
| JPS6021148B2 true JPS6021148B2 (en) | 1985-05-25 |
Family
ID=13141777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6042376A Expired JPS6021148B2 (en) | 1976-05-25 | 1976-05-25 | New optically active pyridinium salt and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6021148B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4916775B2 (en) * | 2006-05-31 | 2012-04-18 | 京セラキンセキ株式会社 | Piezoelectric oscillator |
-
1976
- 1976-05-25 JP JP6042376A patent/JPS6021148B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52144673A (en) | 1977-12-02 |
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