JPS63427B2 - - Google Patents
Info
- Publication number
- JPS63427B2 JPS63427B2 JP742882A JP742882A JPS63427B2 JP S63427 B2 JPS63427 B2 JP S63427B2 JP 742882 A JP742882 A JP 742882A JP 742882 A JP742882 A JP 742882A JP S63427 B2 JPS63427 B2 JP S63427B2
- Authority
- JP
- Japan
- Prior art keywords
- adpe
- salt
- optical purity
- methanol
- meoh
- 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
- 230000003287 optical effect Effects 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 7
- -1 erythro-2-amino-1,2-diphenylethanol cinnamates Chemical class 0.000 claims description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- GEJJWYZZKKKSEV-UHFFFAOYSA-N 2-amino-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(N)C(O)C1=CC=CC=C1 GEJJWYZZKKKSEV-UHFFFAOYSA-N 0.000 claims 1
- 229940114081 cinnamate Drugs 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 90
- 150000003839 salts Chemical class 0.000 description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 239000012452 mother liquor Substances 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010908 decantation Methods 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006345 epimerization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000006340 racemization Effects 0.000 description 2
- GEJJWYZZKKKSEV-UONOGXRCSA-N (1r,2s)-2-amino-1,2-diphenylethanol Chemical compound C1([C@@H](O)[C@@H](N)C=2C=CC=CC=2)=CC=CC=C1 GEJJWYZZKKKSEV-UONOGXRCSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 235000001258 Cinchona calisaya Nutrition 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- QMGVPVSNSZLJIA-UHFFFAOYSA-N Nux Vomica Natural products C1C2C3C4N(C=5C6=CC=CC=5)C(=O)CC3OCC=C2CN2C1C46CC2 QMGVPVSNSZLJIA-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- WAKHLWOJMHVUJC-UHFFFAOYSA-N benzoin alpha-oxime Natural products C=1C=CC=CC=1C(=NO)C(O)C1=CC=CC=C1 WAKHLWOJMHVUJC-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明は（±）−エリトロ−２−アミノ−１・
２−ジフエニルエタノールの光学分割法に関する
ものである。本発明方法によつて得られるエリト
ロ−２−アミノ−１・２−ジフエニルエタノール
（以下ADPEと略記する）はエフエドリン、キニ
ーネ、ストリキニーネあるいは天然α−アミノ酸
を還元して得られるアミノアルコールなどの天然
分割剤の欠点を補う純合成塩基性分割剤として有
用な化合物と期待される。DETAILED DESCRIPTION OF THE INVENTION The present invention provides (±)-erythro-2-amino-1.
This invention relates to an optical resolution method for 2-diphenylethanol. Erythro-2-amino-1,2-diphenylethanol (hereinafter abbreviated as ADPE) obtained by the method of the present invention is a natural alcohol such as efuedrine, quinine, strychnine, or an amino alcohol obtained by reducing natural α-amino acids. It is expected to be a useful compound as a purely synthetic basic resolving agent that compensates for the drawbacks of resolving agents.
本発明者らは、このような観点から光学活性
ADPEを塩基性分割剤として利用すべく、当該化
合物の光学分割について検討した。光学活性
ADPEを取得する方法としては、（±）−ADPEを
Ｌ−グルタミン酸との塩に導き、その塩を通常の
ジアステレオマー法によつて分別結晶する方法
〔J.Weijland、K.Pfister.3rd、E.F.Swanezy、C.
A Robinson、and M.Tishler、J.Am.Chem.
Soc.、73、1216（1951）．〕が知られているが、高
い光学純度のADPEを得るためには再結晶をくり
返す必要があり、また両方の活性体を高い光学純
度で得ることが困難であるなどの難点を有してい
る。 From this perspective, the present inventors have investigated optical activity.
In order to utilize ADPE as a basic resolving agent, we investigated the optical resolution of the compound. optical activity
As a method for obtaining ADPE, (±)-ADPE is converted into a salt with L-glutamic acid, and the salt is fractionally crystallized by the usual diastereomer method [J. Weijland, K. Pfister. 3rd, EFSwanezy, C.
A Robinson, and M. Tishler, J. Am. Chem.
Soc., 73 , 1216 (1951). ], but it has the disadvantages that it is necessary to repeat recrystallization to obtain ADPE with high optical purity, and it is difficult to obtain both active forms with high optical purity. There is.
そこで、本発明者らはADPEの、より簡便で効
率の良い分割法について種々検討した結果、（±）
−ADPEのケイ皮酸（以下CAと略記する）塩と
光学活性ADPEのCA塩との間に大きな溶解度差
が認められることに注目し、当該塩の優先晶出法
による光学分割を種々試みた。その結果、（±）−
ADPE・CA塩の過飽和溶液あるいはいずれか一
方の光学活性ADPE・CA塩を過剰に含む過飽和
溶液に種晶を接種することによつて（＋）−ある
いは（−）−ADPE・CA塩が極めて効率良くしか
も高い光学純度で得られ、これらの塩を常法に従
いアルカリで分解するとラセミ化あるいはエピメ
リ化を伴うことなく光学活性ADPEを取得できる
ことを見い出し、本発明を完成させた。 Therefore, as a result of various studies on simpler and more efficient dividing methods for ADPE, the present inventors found that (±)
-Noting that there is a large solubility difference between the cinnamic acid (hereinafter abbreviated as CA) salt of ADPE and the CA salt of optically active ADPE, we attempted various optical resolutions of the salt using preferential crystallization methods. . As a result, (±)−
By inoculating seed crystals into a supersaturated solution of ADPE/CA salt or a supersaturated solution containing an excess of either optically active ADPE/CA salt, (+)- or (-)-ADPE/CA salt can be produced with extremely high efficiency. The present inventors have completed the present invention by discovering that optically active ADPE can be obtained with good optical purity and that optically active ADPE can be obtained without racemization or epimerization by decomposing these salts with an alkali according to a conventional method.
本発明を実施するにあたつてその原料となる
（±）−ADPEはベンゾインα−オキシムをパラジ
ウム−炭素を用いて接触還元することによつて容
易に、かつ大量に合成することができる。この
（±）−ADPEにメタノールあるいはエタノール中
で等モル量のCAを作用させ、（±）−ADPE・CA
塩を調製する。このようにして得た（±）−
ADPE・CA塩をメタノール、エタノール、２−
プロパノールなどの有機溶剤に加温溶解した後、
徐冷して過飽和溶液となし、（＋）−あるいは
（−）−ADPE・CA塩を種晶として接種し、種晶
と同種の光学活性ADPE・CA塩を得る。この母
液に（±）−ADPE・CA塩を補充し過飽和溶液と
なし、前回接種した光学活性体と反対の旋光性を
もつADPE・CA塩を接種して、同種の光学活性
ADPE・CA塩を得る。以下このような操作を繰
り返すことによつてADPE・CA塩の両対掌体を
交互に得ることができる。この時（±）ADPE・
CA塩とともに（±）−ADPEの酢酸あるいは乳酸
塩などこれらの有機溶剤に可溶な塩を共存させる
と、安定した収量、光学純度で光学活性ADPE・
CA塩が得られる。 (±)-ADPE, which is a raw material for carrying out the present invention, can be easily synthesized in large quantities by catalytic reduction of benzoin α-oxime using palladium-carbon. This (±)-ADPE was treated with an equimolar amount of CA in methanol or ethanol, and (±)-ADPE・CA
Prepare salt. Obtained in this way (±)−
ADPE・CA salt in methanol, ethanol, 2-
After heating and dissolving in an organic solvent such as propanol,
It is slowly cooled to form a supersaturated solution, and (+)- or (-)-ADPE/CA salt is inoculated as a seed crystal to obtain an optically active ADPE/CA salt of the same type as the seed crystal. This mother liquor was supplemented with (±)-ADPE・CA salt to make a supersaturated solution, and an ADPE・CA salt with optical rotation opposite to that of the previously inoculated optically active substance was inoculated to obtain the same optical activity.
Obtain ADPE/CA salt. By repeating such operations, both enantiomers of ADPE/CA salt can be obtained alternately. At this time (±)ADPE・
When a salt soluble in these organic solvents, such as acetic acid or lactate of (±)-ADPE, coexists with CA salt, optically active ADPE can be produced with stable yield and optical purity.
CA salt is obtained.
さらに、本法により低光学純度のADPEを精製
することができる。すなわち、低光学純度の
ADPEをCA塩となし、この塩の過飽和溶液に過
剰に含まれる方の光学活性ADPE・CA塩と同種
の光学活性ADPE・CA塩を種晶として接種する
かあるいは接種することなしに過剰に含まれる方
の光学活性はADPE・CA塩を得ることができる。 Furthermore, ADPE with low optical purity can be purified by this method. That is, low optical purity
ADPE is used as a CA salt, and an optically active ADPE/CA salt of the same kind as the optically active ADPE/CA salt contained in excess is inoculated as a seed crystal in a supersaturated solution of this salt, or an excess is added without inoculation. The optical activity of the ADPE/CA salt can be obtained.
このようにして得た光学活性ADPE・CA塩は
光学純度が高く、ほとんど１回の再結晶により、
光学的に純粋な（＋）−または（−）−ADPE・
CA塩を得ることができる。この塩を常法に従い
アルカリで分解するとラセミ化あるいはエピメリ
化を伴うことなく、光学的に純粋なADPEが得ら
れる。 The optically active ADPE/CA salt obtained in this way has high optical purity, and can be obtained by almost one recrystallization.
Optically pure (+)- or (-)-ADPE・
CA salt can be obtained. When this salt is decomposed with an alkali according to a conventional method, optically pure ADPE can be obtained without racemization or epimerization.
次に、本発明を実施例により、さらに詳細に説
明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
（±）−ADPE・CA塩4.50ｇ、（−）−ADPE・
CA塩0.21ｇおよび（±）−ADPE・乳酸塩6.00ｇ
をメタノール110mlに加熱溶解した後室温まで放
冷し、（−）−ADPE・CA塩（mp172〜173℃、
〔α〕30 435−170.7゜（c0.60、99％MeOH））20mgを接
種し、約５℃で３時間静置した後、デカンテーシ
ヨンにより母液を分離すると（−）−ADPE・CA
塩が得られる。収量0.77ｇ、〔α〕435−167.8゜
（c0.60、99％MeOH）、光学純度98％
次に、母液に（±）−ADPE・CA塩0.70ｇを加
え加熱溶解し、（＋）−ADPE・CA塩（mp172〜
173℃、〔α〕30 435＋170.7゜（c0.60、99％MeOH））20
mgを接種して同様に操作することにより、（＋）−
ADPE・CA塩が得られる。収量0.45ｇ、〔α〕435
＋161.2゜（c0.60、99％MeOH）、光学純度94％
以下同様の操作を繰返すことにより、毎回0.5
〜0.8ｇの収量で光学純度95〜98％の光学活性
ADPE・CA塩が得られる。Example 1 (±)-ADPE・CA salt 4.50g, (−)-ADPE・
CA salt 0.21g and (±)-ADPE lactate 6.00g
After heating and dissolving in 110 ml of methanol, it was allowed to cool to room temperature, and (-)-ADPE・CA salt (mp172-173℃,
[α] 30 435 −170.7゜(c0.60, 99% MeOH)) 20mg was inoculated, left to stand at about 5℃ for 3 hours, and the mother liquor was separated by decantation, resulting in (−)−ADPE・CA
Salt is obtained. Yield 0.77 g, [α] 435 −167.8° (c 0.60, 99% MeOH), optical purity 98% Next, (±)-ADPE・CA salt 0.70 g was added to the mother liquor and dissolved by heating, (+)- ADPE/CA salt (mp172~
173℃, [α] 30 435 +170.7゜ (c0.60, 99%MeOH)) 20
By inoculating mg and performing the same operation, (+)−
ADPE/CA salt is obtained. Yield 0.45g, [α] 435
+161.2゜(c0.60, 99%MeOH), optical purity 94% Below, by repeating the same operation, each time 0.5
Optical activity with optical purity of 95-98% in ~0.8g yield
ADPE/CA salt is obtained.
このようにして得た光学活性ADPE・CA塩を
同符号同志集めて、メタノールを溶媒として１回
再結晶すると、60〜65％の再結晶収率で光学純度
99％の精製光学活性ADPE・CA塩（mp172〜173
℃、〔α〕435＋および−168.5゜（c0.60、99％
MeOH）が得られる。 When the optically active ADPE/CA salts obtained in this way are collected with the same sign and recrystallized once using methanol as a solvent, optical purity is achieved with a recrystallization yield of 60 to 65%.
99% purified optically active ADPE/CA salt (mp172~173
°C, [α] 435 + and -168.5° (c0.60, 99%
MeOH) is obtained.
実施例 ２
（±）−ADPE・CA塩22.40ｇ、（＋）−
ADPE・CA塩2.17ｇおよび（±）−ADPE・乳酸
塩30.00ｇをメタノール550mlに加熱溶解後徐冷
し、室温で（＋）−ADPE・CA塩40mgを接種し、
ゆつくりと撹拌しながら75分間８℃前後に冷却す
ると、（＋）−ADPE・CA塩の結晶が優先的に晶
出する。母液をデカンテーシヨンにより分け、結
晶は少量のメタノールで洗浄後乾燥すると（＋）
−ADPE・CA塩が得られる。収量5.11ｇ、〔α〕
435＋164.3゜（c0.60、99％MeOH）、光学純度96％
次に、母液に（±）−ADPE・CA塩5.50ｇを追
加して加熱溶解し、（−）−ADPE・CA塩40mgを
接種して同様に操作すると、（−）−ADPE・CA
塩が得られる。収量4.99ｇ、〔α〕435−161.6゜
（c0.60、99％MeOH）、光学純度95％
以下同様の操作を繰返すことにより、毎回4.5
〜5.5ｇの収量で光学純度90〜99％の光学活性
ADPE・CA塩が得られる。Example 2 (±)-ADPE・CA salt 22.40g, (+)-
2.17 g of ADPE/CA salt and 30.00 g of (±)-ADPE/lactate were dissolved by heating in 550 ml of methanol, then slowly cooled, and inoculated with 40 mg of (+)-ADPE/CA salt at room temperature.
When cooled to around 8°C for 75 minutes with gentle stirring, (+)-ADPE/CA salt crystals preferentially crystallize. The mother liquor is separated by decantation, and the crystals are washed with a small amount of methanol and dried (+)
-ADPE/CA salt is obtained. Yield 5.11g, [α]
435 +164.3゜(c0.60, 99% MeOH), optical purity 96% Next, add 5.50 g of (±)-ADPE・CA salt to the mother liquor and dissolve by heating to dissolve (−)-ADPE・CA salt. When inoculated with 40 mg and operated in the same manner, (-)-ADPE・CA
Salt is obtained. Yield: 4.99 g, [α] 435 −161.6° (c0.60, 99% MeOH), optical purity: 95%. By repeating the same operation, each time
Optical activity with optical purity of 90-99% in ~5.5g yield
ADPE/CA salt is obtained.
このようにして得た光学活性ADPE・CA塩の
同符号同志を集め、メタノールを溶媒として１回
再結晶すると、光学純度99％以上の精製光学活性
ADPE・CA塩（mp172〜173℃、〔α〕435＋168.5゜
および−169.6゜（c0.60、99％MeOH）が60〜65％
の収率で得られる。 When the optically active ADPE/CA salts obtained in this way are collected with the same sign and recrystallized once using methanol as a solvent, purified optical activity with an optical purity of 99% or more is obtained.
ADPE/CA salt (mp172-173℃, [α] 435 +168.5゜ and -169.6゜(c0.60, 99%MeOH) is 60-65%
obtained with a yield of .
これらの塩をそれぞれ常法に従い10％水酸化ナ
トリウム水溶液で分解し、得られる粗ADPEを95
％エタノールを溶媒として用い再結晶すると70〜
80％の収率で精製光学活性ADPEが得られる
（mp141〜144℃、〔α〕589＋7.7゜および−7.6゜
（c0.60、abs.EtOH））。 Each of these salts is decomposed with a 10% aqueous sodium hydroxide solution according to a conventional method, and the resulting crude ADPE is
70 ~ when recrystallized using ethanol as a solvent
Purified optically active ADPE is obtained with a yield of 80% (mp 141-144°C, [α] 589 +7.7° and -7.6° (c0.60, abs.EtOH)).
実施例 ３
（±）−ADPE・CA塩22.40ｇ及び（±）−
ADPE・乳酸塩30.00ｇをメタノール550mlに加熱
溶解後徐冷し、室温で（−）−ADPE・CA塩100
mgを接種し、ゆつくりと撹拌しながら60分間５℃
前後に冷却すると、（−）−ADPE・CA塩の結晶
が優先的に晶出する。母液をデカンテーシヨンに
より分け、結晶は少量のメタノールで洗浄後乾燥
すると（−）−ADPE・CA塩が得られる。収量
3.84ｇ、〔α〕435−163.3゜（c0.60、99％MeOH）光
学純度95％。Example 3 (±)-ADPE・CA salt 22.40g and (±)-
Dissolve 30.00 g of ADPE/lactate in 550 ml of methanol by heating, then slowly cool at room temperature (-)-ADPE/CA salt 100
inoculated with 5°C for 60 minutes with gentle stirring.
When cooled back and forth, (-)-ADPE/CA salt crystals preferentially crystallize. The mother liquor is separated by decantation, and the crystals are washed with a small amount of methanol and dried to obtain (-)-ADPE/CA salt. yield
3.84 g, [α] 435 −163.3° (c0.60, 99% MeOH) optical purity 95%.
これをメタノール45mlで再結晶すると光学純度
99％以上の精製（−）−ADPE・CA塩が2.91ｇ得
られる。mp172〜173℃、〔α〕435−169.2゜（c0.60、
99％MeOH）
精製塩を常法に従い10％水酸化ナトリウム水溶
液で分解し、得られる粗ADPEを95％エタノール
15mlで再結晶すると精製（−）−ADPEが1.44ｇ
得られる。mp141−143℃、〔α〕589−7.5゜（c0.60、
abs.EtOH）。 When this is recrystallized with 45 ml of methanol, optical purity is obtained.
2.91 g of 99% or more purified (-)-ADPE/CA salt is obtained. mp172~173℃, [α] 435 −169.2゜(c0.60,
99% MeOH) The purified salt was decomposed with a 10% aqueous sodium hydroxide solution according to a conventional method, and the resulting crude ADPE was dissolved in 95% ethanol.
When recrystallized in 15 ml, purified (-)-ADPE is 1.44 g.
can get. mp141−143℃, [α] 589 −7.5゜(c0.60,
abs.EtOH).
実施例 ４
光学純度60％のADPE・CA塩（（＋）−
ADPE・CA塩を80％、（−）−ADPE・CA塩を20
％含む）10.00ｇをメタノール250mlに加熱溶解後
徐冷し、室温で（＋）−ADPE・CA塩40mgを接種
し、ゆつくりと撹拌しながら75分間10℃前後に冷
却すると（＋）−ADPE・CA塩の結晶が優先的に
晶出する。母液をデカンテーシヨンにより分け、
結晶は少量のメタノールで洗浄後乾燥すると
（＋）−ADPE・CA塩が得られる。収量7.22ｇ、
〔α〕435＋164.8゜（c0.60、99％、MeOH）、光学純
度96％。Example 4 ADPE/CA salt with optical purity of 60% ((+)-
ADPE/CA salt 80%, (-)-ADPE/CA salt 20%
%) was heated and dissolved in 250 ml of methanol, then slowly cooled, inoculated with 40 mg of (+)-ADPE/CA salt at room temperature, and cooled to around 10°C for 75 minutes with gentle stirring to form (+)-ADPE.・Crystals of CA salt crystallize preferentially. The mother liquor is separated by decantation,
When the crystals are washed with a small amount of methanol and dried, (+)-ADPE/CA salt is obtained. Yield 7.22g,
[α] 435 +164.8° (c0.60, 99%, MeOH), optical purity 96%.
これをメタノール100mlで再結晶すると光学純
度99％以上の精製（＋）−ADPE・CA塩が5.31ｇ
得られる。mp172〜173℃、〔α〕435＋169.9゜
（c0.60、99％MeOH）。 When this is recrystallized with 100ml of methanol, 5.31g of purified (+)-ADPE/CA salt with optical purity of 99% or more is obtained.
can get. mp172-173℃, [α] 435 +169.9゜ (c0.60, 99% MeOH).
精製塩を常法に従い10％水酸化ナトリウム水溶
液で分解し、得られる粗ADPEを95％エタノール
25mlで再結晶すると精製（＋）−ADPEが2.61ｇ
得られる。mp142〜144℃、〔α〕589＋7.6゜（c0.60、
abs.EtOH）。 Purified salt is decomposed with a 10% aqueous sodium hydroxide solution according to a conventional method, and the resulting crude ADPE is dissolved in 95% ethanol.
When recrystallized in 25ml, purified (+)-ADPE is 2.61g
can get. mp142~144℃, [α] 589 +7.6゜(c0.60,
abs.EtOH).
実施例 ５
光学純度74％のADPE・CA塩（（＋）−
ADPE・CA塩を87％、（−）−ADPE・CA塩を13
％含む）30.00ｇをメタノール1000mlに加熱溶解
後徐冷し、室温で一昼夜静置すると（＋）−
ADPE・CA塩の結晶が優先的に晶出する。母液
をデカンテーシヨンにより分け、結晶は少量のメ
タノールで洗浄後乾燥すると（＋）−ADPE・CA
塩が得られる。収量14.86ｇ、〔α〕435＋165.2゜
（c0.60、99％MeOH）、光学純度97％。Example 5 ADPE/CA salt with optical purity of 74% ((+)-
ADPE・CA salt 87%, (−)−ADPE・CA salt 13%
When 30.00g (containing %) was heated and dissolved in 1000ml of methanol, cooled slowly and left at room temperature overnight, (+)-
ADPE/CA salt crystals are preferentially crystallized. The mother liquor is separated by decantation, and the crystals are washed with a small amount of methanol and dried to form (+)-ADPE・CA.
Salt is obtained. Yield 14.86 g, [α] 435 +165.2° (c 0.60, 99% MeOH), optical purity 97%.
これをメタノール200mlで再結晶すると光学純
度99％以上の精製（＋）−ADPE・CA塩が10.13
ｇ得られる。mp172〜173℃、〔α〕435＋169.4゜
（c0.60、99％MeOH）。 When this is recrystallized with 200 ml of methanol, purified (+)-ADPE/CA salt with optical purity of 99% or more is obtained at 10.13
g can be obtained. mp172-173℃, [α] 435 +169.4゜ (c0.60, 99% MeOH).
精製塩を常法に従い10％水酸化ナトリウム水溶
液で分解し、得られる粗ADPEを95％エタノール
50mlで再結晶すると精製（＋）−ADPEが4.98ｇ
得られる。mp143〜144℃、〔α〕589＋7.6゜（c0.60、
abs.EtOH）。 Purified salt is decomposed with a 10% aqueous sodium hydroxide solution according to a conventional method, and the resulting crude ADPE is dissolved in 95% ethanol.
When recrystallized in 50ml, purified (+)-ADPE is 4.98g
can get. mp143~144℃, [α] 589 +7.6゜(c0.60,
abs.EtOH).
Claims (1)
フエニルエタノール・ケイ皮酸塩の過飽和溶液
に、いずれか一方の光学活性エリトロ−２−アミ
ノ−１・２−ジフエニルエタノール・ケイ皮酸塩
の結晶を接種して、同種の光学活性体を優先的に
晶出させることを特徴とする、（±）−エリトロ−
２−アミノ−１・２−ジフエニルエタノールの光
学分割法。1 Add one of the optically active erythro-2-amino-1,2-diphenylethanol cinnamates to a supersaturated solution of (±)-erythro-2-amino-1,2-diphenylethanol cinnamate. (±)-Erythro-
Optical resolution method of 2-amino-1,2-diphenylethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP742882A JPS58124749A (en) | 1982-01-22 | 1982-01-22 | Optical resolution of (+-)-2-amino-1,2-diphenyl ethanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP742882A JPS58124749A (en) | 1982-01-22 | 1982-01-22 | Optical resolution of (+-)-2-amino-1,2-diphenyl ethanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58124749A JPS58124749A (en) | 1983-07-25 |
| JPS63427B2 true JPS63427B2 (en) | 1988-01-07 |
Family
ID=11665591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP742882A Granted JPS58124749A (en) | 1982-01-22 | 1982-01-22 | Optical resolution of (+-)-2-amino-1,2-diphenyl ethanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58124749A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10604452B2 (en) | 2004-11-12 | 2020-03-31 | General Electric Company | Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix |
-
1982
- 1982-01-22 JP JP742882A patent/JPS58124749A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10604452B2 (en) | 2004-11-12 | 2020-03-31 | General Electric Company | Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58124749A (en) | 1983-07-25 |
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