JPH053865B2 - - Google Patents
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- Publication number
- JPH053865B2 JPH053865B2 JP1781085A JP1781085A JPH053865B2 JP H053865 B2 JPH053865 B2 JP H053865B2 JP 1781085 A JP1781085 A JP 1781085A JP 1781085 A JP1781085 A JP 1781085A JP H053865 B2 JPH053865 B2 JP H053865B2
- Authority
- JP
- Japan
- Prior art keywords
- dimethylcyclopropylamine
- optically active
- carboxamide
- dimethylcyclopropane
- yield
- 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 - Lifetime
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、式
で示される光学活性２，２−ジメチルシクロプロ
ピルアミンおよびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the formula The present invention relates to an optically active 2,2-dimethylcyclopropylamine represented by and a method for producing the same.
本発明における上記式で示される光学活性な
２，２−ジメチルシクロプロピルアミンはこれま
で全く知られておらず、本発明者らが初めて合成
した文献末記載の新規化合物であつて、該化合物
は医薬あるいは農業用の中間体として有用である
のみならず、他の光学活性アミンに比べて低沸点
であり、光学異性体分離試薬あるいは光学純度測
定のための試薬として利用することができる。 The optically active 2,2-dimethylcyclopropylamine represented by the above formula in the present invention has not been known at all, and is a new compound synthesized by the present inventors for the first time and described at the end of the literature. It is not only useful as a pharmaceutical or agricultural intermediate, but also has a lower boiling point than other optically active amines, and can be used as an optical isomer separation reagent or a reagent for measuring optical purity.
かかる光学活性な２，２−ジメチルシクロプロ
ピルアミンは式
で示される光学活性な２，２−ジメチルシクロプ
ロパン−１−カルボキサミドを、アルカリの存在
下、次亜塩素酸ソーダ、塩素および臭素から選ば
れる１種と反応させるいわゆるホフマン分解によ
り、ラセミ化することなく収率よく製造すること
ができる。 Such optically active 2,2-dimethylcyclopropylamine has the formula Racemization of the optically active 2,2-dimethylcyclopropane-1-carboxamide shown by the so-called Hofmann decomposition, in which the optically active 2,2-dimethylcyclopropane-1-carboxamide is reacted with one selected from sodium hypochlorite, chlorine, and bromine in the presence of an alkali. It can be produced with good yield without any problems.
ここで、原料となる光学活性な２，２−ジメチ
ルシクロプロパン−１−カルボキサミドは公知化
合物であり、たとえば特開昭55−51023号公報に
記載の方法により製造することができる。 The optically active 2,2-dimethylcyclopropane-1-carboxamide used as a raw material is a known compound, and can be produced, for example, by the method described in JP-A-55-51023.
この反応において使用されるアルカリとしては
水酸化ナトリウム、水酸化カリウム、水酸化カル
シウムなどが例示され、その使用量は原料カルボ
キサミドに対して４倍モル以上、通常は４〜５モ
ルである。 Examples of the alkali used in this reaction include sodium hydroxide, potassium hydroxide, calcium hydroxide, etc., and the amount used is at least 4 times the mole of the raw material carboxamide, usually 4 to 5 moles.
かかるアルカリは水溶液として使用され、その
濃度については特に制限されないが、好ましくは
10重量％以上である。 Such an alkali is used as an aqueous solution, and its concentration is not particularly limited, but preferably
It is 10% by weight or more.
また、次亜塩素酸ソーダ、塩素または臭素は原
料カルボキサミドに対して１倍モル以上、好まし
くは１〜1.5倍モル使用され、その使用方法とし
て次亜塩素酸ソーダを使用する場合には水溶液好
ましくは濃度５重量％以上の水溶液として使用さ
れ、塩素の場合には塩素ガスを反応系へ吹き込む
ことにより使用される。 In addition, sodium hypochlorite, chlorine, or bromine is used in an amount of 1 mole or more, preferably 1 to 1.5 times the mole of the raw material carboxamide, and when using sodium hypochlorite, an aqueous solution is preferably used. It is used as an aqueous solution with a concentration of 5% by weight or more, and in the case of chlorine, it is used by blowing chlorine gas into the reaction system.
反応温度は通常−20℃〜100℃、好ましくは−
10℃〜80℃である。 The reaction temperature is usually -20°C to 100°C, preferably -
The temperature is between 10°C and 80°C.
かくして、本発明の方法により、原料光学活性
体に応じてＳ（−）−２，２−ジメチルシクロプロ
ピルアミンまたはＲ（＋）−２，２−ジメチルシク
ロプロピルアミンを容易に得ることができる。 Thus, according to the method of the present invention, S(-)-2,2-dimethylcyclopropylamine or R(+)-2,2-dimethylcyclopropylamine can be easily obtained depending on the optically active material as a raw material.
以下、実施例により本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 １
Ｓ（＋）２，２−ジメチルシクロプロパン−１
−カルボキサミド113.2g（１モル）、20％水酸化ナ
トリウム水溶液800gをフラスコに仕込み、35〜
40℃にて13％次亜塩素酸ソーダ水溶液860gを２
時間で滴下し、２時間保温したのち、過剰の次亜
塩素酸ソーダを亜硫酸ソーダにて不活性とする。Example 1 S(+)2,2-dimethylcyclopropane-1
-Pour 113.2g (1 mol) of carboxamide and 800g of 20% sodium hydroxide aqueous solution into a flask, and
860g of 13% sodium hypochlorite aqueous solution at 40℃
After dropping the solution for 2 hours and keeping it warm for 2 hours, excess sodium hypochlorite is inactivated with sodium sulfite.
この反応液を蒸留して、生成したＳ（−）−２，
２−ジメチルシクロプロピルアミンを留出させ、
さらに精留して精製を行つた。 This reaction solution was distilled to produce S(-)-2,
Distilling 2-dimethylcyclopropylamine,
Further purification was carried out by rectification.
収量 49.4g（収率58.0％）
bp 84〜85℃
n25 D 1.4197
α〕25 365＝−42.1°（ｃ＝１，エタノール）
実施例 ２
原料としてＳ（＋）−２，２−ジメチルシクロプ
ロパン−１−カルボキサミド113.2g（１モル）（光
学純度85％）使用する以外は実施例１と同様にし
てＳ（−）−２，２−ジメチルシクロプロピルアミ
ン48.5g（収率57.0％）を得た。 Yield 49.4g (yield 58.0%) bp 84-85℃ n 25 D 1.4197 α] 25 365 = -42.1° (c = 1, ethanol) Example 2 S(+)-2,2-dimethylcyclopropane as a raw material -48.5 g (yield 57.0%) of S(-)-2,2-dimethylcyclopropylamine was obtained in the same manner as in Example 1 except that 113.2 g (1 mol) (optical purity 85%) of -1-carboxamide was used. Ta.
α〕25 365＝−35.6°（ｃ＝１，エタノール）
光学純度84.5％
実施例 ３
原料としてＲ（−）−２，２−ジメチルシクロプ
ロパン−１−カルボキサミド113.2g（１モル）を
使用する以外は実施例１と同様にしてＲ（＋）−
２，２−ジメチル−シクロプロピルアミン50.5g
（収率59.3％）を得た。 α〕 25 365 = -35.6° (c = 1, ethanol) Optical purity 84.5% Example 3 Except for using 113.2 g (1 mol) of R(-)-2,2-dimethylcyclopropane-1-carboxamide as a raw material is R(+)− in the same manner as in Example 1.
2,2-dimethyl-cyclopropylamine 50.5g
(yield 59.3%).
α〕25 365＝＋42.1°（ｃ＝１，エタノール）
b.p 84〜85.5℃
n25 D 1.4196
実施例 ４
Ｓ（＋）−２，２−ジメチルシクロプロパン−１
−カルボキサミド113.2g（１モル）および20％水
酸化ナトリウム水溶液800gをフラスコに仕込み、
０〜５℃にて塩素ガス106.4g（1.5モル）を吹き込
んだのち２時間保温する。 α] 25 365 = +42.1° (c = 1, ethanol) bp 84-85.5°C n 25 D 1.4196 Example 4 S(+)-2,2-dimethylcyclopropane-1
- Charge 113.2 g (1 mol) of carboxamide and 800 g of 20% aqueous sodium hydroxide solution into a flask,
After blowing 106.4 g (1.5 mol) of chlorine gas at 0 to 5°C, the mixture is kept warm for 2 hours.
この反応液を実施例１と同様に蒸留、精留して
Ｓ（−）−２，２−ジメチルシクロプロピルアミン
74.5g（収率87.5％）を得た。 This reaction solution was distilled and rectified in the same manner as in Example 1 to obtain S(-)-2,2-dimethylcyclopropylamine.
74.5g (yield 87.5%) was obtained.
実施例 ５
塩素ガスを吹き込む代わりに臭素239.7g（1.5モ
ル）を滴下する以外は実施例４と同様にしてＳ
（−）−２，２−ジメチルシクロプロピルアミン
79.3g（収率93.2％）を得た。Example 5 S was prepared in the same manner as in Example 4 except that 239.7 g (1.5 mol) of bromine was added dropwise instead of blowing in chlorine gas.
(-)-2,2-dimethylcyclopropylamine
79.3g (yield 93.2%) was obtained.
Claims (1)
ピルアミン ２ 式 で示される光学活性な２，２−ジメチルシクロプ
ロパン−１−カルボキサミドをアルカリの存在
下、次亜塩素酸ソーダ、塩素および臭素から選ば
れる１種と反応させることを特徴とする式 で示される光学活性２、２−ジメチルシクロプロ
ピルアミンの製造方法。[Claims] 1 set Optically active 2,2-dimethylcyclopropylamine 2 represented by the formula A formula characterized by reacting optically active 2,2-dimethylcyclopropane-1-carboxamide represented by with one selected from sodium hypochlorite, chlorine and bromine in the presence of an alkali. A method for producing optically active 2,2-dimethylcyclopropylamine shown by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1781085A JPS61176557A (en) | 1985-01-31 | 1985-01-31 | Optically active 2,2-dimethylcyclopropylamine and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1781085A JPS61176557A (en) | 1985-01-31 | 1985-01-31 | Optically active 2,2-dimethylcyclopropylamine and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61176557A JPS61176557A (en) | 1986-08-08 |
| JPH053865B2 true JPH053865B2 (en) | 1993-01-18 |
Family
ID=11954082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1781085A Granted JPS61176557A (en) | 1985-01-31 | 1985-01-31 | Optically active 2,2-dimethylcyclopropylamine and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61176557A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0615620D0 (en) * | 2006-08-05 | 2006-09-13 | Astrazeneca Ab | A process for the preparation of optically active intermediates |
-
1985
- 1985-01-31 JP JP1781085A patent/JPS61176557A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61176557A (en) | 1986-08-08 |
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