JP3503993B2 - Method for producing N-mono-t-butyloxycarbonylalkylenediamine - Google Patents
Method for producing N-mono-t-butyloxycarbonylalkylenediamineInfo
- Publication number
- JP3503993B2 JP3503993B2 JP19938594A JP19938594A JP3503993B2 JP 3503993 B2 JP3503993 B2 JP 3503993B2 JP 19938594 A JP19938594 A JP 19938594A JP 19938594 A JP19938594 A JP 19938594A JP 3503993 B2 JP3503993 B2 JP 3503993B2
- Authority
- JP
- Japan
- Prior art keywords
- mono
- butyloxycarbonylalkylenediamine
- producing
- range
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、医薬、農薬などの中間
体として有用な下記一般式〔２〕で示されるＮ−モノ−
ｔ−ブチルオキシカルボニルアルキレンジアミンの製造
法に関する。FIELD OF THE INVENTION The present invention is useful as an intermediate for medicines, agricultural chemicals and the like, represented by the following general formula [2]: N-mono-
The present invention relates to a method for producing t-butyloxycarbonylalkylenediamine.
【０００２】[0002]
【従来の技術】従来、一般式〔２〕で示されるＮ−モノ
−ｔ−ブチルオキシカルボニルアルキレンジアミンの製
造法は、例えば、特開昭６４−２６５４７号公報の実施
例１にジ（ｔ−ブチル）ジカーボネートに４倍モルの
Ｎ，Ｎ’−ジメチルエチレンジアミンを反応させる方法
が記載されている。2. Description of the Related Art Conventionally, a method for producing N-mono-t-butyloxycarbonylalkylenediamine represented by the general formula [2] is described in, for example, Example 1 of JP-A No. 64-26547 and di (t- A method is described in which butyl) dicarbonate is reacted with 4 times the molar amount of N, N′-dimethylethylenediamine.
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記の方法に
おいては、Ｎ，Ｎ’−ジメチルエチレンジアミンを多量
に使用しなければならず、過剰のＮ，Ｎ’−ジメチルエ
チレンジアミンを回収する必要があり工業的製造法とし
ては充分なものとは言い難いものであった。However, in the above method, it is necessary to use a large amount of N, N'-dimethylethylenediamine, and it is necessary to recover an excess of N, N'-dimethylethylenediamine. It was hard to say that it was a sufficient method as a static manufacturing method.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、ジ（ｔ−
ブチル）ジカーボネートに等モルのアルキレンジアミン
を反応させ、副生成物の少ない一般式〔２〕で示される
Ｎ−モノ−ｔ−ブチルオキシカルボニルアルキレンジア
ミンの製造法について検討した結果、本発明に至った。
すなわち、本発明は、水−親水性溶媒系で、一般式
〔１〕
（式中、Ｒは、水素原子または低級アルキル基を示し、
ｎは、１〜３の整数を示す。）で示されるアルキレンジ
アミンに酸を作用させ、次いでジ−ｔ−ブチルジカーボ
ネートをｐＨ４〜８の範囲で反応させることを特徴とす
る一般式〔２〕
（式中、Ｒおよびｎは、前記と同じ意味を表わす。）で
示されるＮ−モノ−ｔ−ブチルオキシカルボニルアルキ
レンジアミンの製造法を提供するものである。DISCLOSURE OF THE INVENTION The present inventors have found that di (t-
Butyl) dicarbonate was reacted with an equimolar amount of alkylenediamine to examine a method for producing N-mono-t-butyloxycarbonylalkylenediamine represented by the general formula [2] with less byproducts, and as a result, the present invention was achieved. It was
That is, the present invention is a water-hydrophilic solvent system and has the general formula [1] (In the formula, R represents a hydrogen atom or a lower alkyl group,
n shows the integer of 1-3. ), An acid is allowed to act on the alkylenediamine, and then di-t-butyldicarbonate is reacted in a pH range of 4 to 8 [2]. (In the formula, R and n have the same meanings as described above.) A method for producing N-mono-t-butyloxycarbonylalkylenediamine is provided.
【０００５】以下、本発明を詳細に説明する。本発明に
用いられる酸としては、一般的な無機および有機酸を挙
げることができ、例えば、塩酸、硫酸、硝酸、燐酸、酢
酸、スルホン酸などが挙げられる。反応系内のｐＨは４
〜８の範囲に保持され、好ましくはｐＨ５〜７の範囲で
ある。このｐＨ調整に用いられる塩基としては、一般的
な無機および有機塩基を挙げることができ、例えば、水
酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭
酸カリウム、トリエチルアミン、トリブチルアミン、テ
トラメチルエチレンジアミンなどが挙げられる。The present invention will be described in detail below. Examples of the acid used in the present invention include general inorganic and organic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and sulfonic acid. PH in the reaction system is 4
It is maintained in the range of ~ 8, preferably in the range of pH 5 ~ 7. Examples of the base used for the pH adjustment include general inorganic and organic bases, and examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, tributylamine, and tetramethylethylenediamine. To be
【０００６】本反応には、水と親水性溶媒との混合溶媒
が用いられ、かかる溶媒としては通常の親水性溶媒が挙
げられ、例えば、メタノール、イソプロパノール、テト
ラヒドロフラン等が挙げられる。該溶媒の使用量は、通
常、アルキレンジアミンに対し通常、２〜５０重量倍で
ある。反応温度は、通常、０〜４０℃の範囲であり、好
ましくは、１０〜３０℃の範囲である。反応時間は、特
には限定されないが、通常、０．５〜８時間で目的を達
することができる。In this reaction, a mixed solvent of water and a hydrophilic solvent is used, and examples of such a solvent include ordinary hydrophilic solvents such as methanol, isopropanol and tetrahydrofuran. The amount of the solvent used is usually 2 to 50 times by weight that of the alkylenediamine. The reaction temperature is usually in the range of 0 to 40 ° C, preferably 10 to 30 ° C. The reaction time is not particularly limited, but usually the purpose can be reached in 0.5 to 8 hours.
【０００７】[0007]
【発明の効果】本発明によれば、Ｎ−モノ−ｔ−ブチル
オキシカルボニルアルキレンジアミンが選択的に製造さ
れることから工業的に有利な方法である。Industrial Applicability According to the present invention, N-mono-t-butyloxycarbonylalkylenediamine is selectively produced, which is an industrially advantageous method.
【０００８】[0008]
【実施例】以下に実施例をあげ本発明をより詳細に説明
するが、本発明はこの実施例に限定されるものではな
い。
（実施例１）水２５ｇ、Ｎ，Ｎ’−ジメチルエチレンジ
アミン２２．９ｇ（０．２４ｍｏｌ）およびメタノール
５０ｇを加え、窒素気流下０〜５℃に冷却し、１０分間
攪拌した。次に、水７５ｇに３６％塩酸２５．４ｇ
（０．２４ｍｏｌ）を溶かした溶液を加え同温度で１０
分間攪拌した。次に、３６％塩酸２０〜３０ｇをｐＨ
６．０になるまで加え、同温度で１０分間攪拌した。次
いで、２０〜２５℃で攪拌下に、メタノール４０ｇにジ
−ｔ−ブチルジカーボネート（ＤＢＣ）５２．４ｇ
（０．２４ｍｏｌ）を溶かした溶液を４時間かけて滴下
した。この際、反応系のｐＨを５．７±１の範囲に保持
するために２０％の水酸化ナトリウム水溶液を滴下し
た。反応後、反応液をサンプリングしてガスクロマトグ
ラフィーで分析したところ、目的物のＮ−ｔ−ブチルオ
キシカルボニル−Ｎ，Ｎ’−ジメチルエチレンジアミン
（モノＢＯＣ体）の反応収率は７０％であり、副生物の
Ｎ，Ｎ’−ジ−ｔ−ブチルオキシカルボニル−Ｎ，Ｎ’
−ジメチルエチレンジアミン（ジＢＯＣ体）の反応収率
は３０％であった。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. (Example 1) 25 g of water, 22.9 g (0.24 mol) of N, N'-dimethylethylenediamine and 50 g of methanol were added, and the mixture was cooled to 0 to 5 ° C under a nitrogen stream and stirred for 10 minutes. Next, 25.4 g of 36% hydrochloric acid in 75 g of water
(0.24 mol) was added and the solution was added at the same temperature for 10
Stir for minutes. Then, add 20% to 30 g of 36% hydrochloric acid to pH.
The mixture was added until it reached 6.0 and stirred at the same temperature for 10 minutes. Then, with stirring at 20 to 25 ° C., 52.4 g of di-t-butyl dicarbonate (DBC) in 40 g of methanol.
A solution of (0.24 mol) was added dropwise over 4 hours. At this time, a 20% aqueous sodium hydroxide solution was added dropwise to keep the pH of the reaction system within the range of 5.7 ± 1. After the reaction, when the reaction solution was sampled and analyzed by gas chromatography, the reaction yield of Nt-butyloxycarbonyl-N, N′-dimethylethylenediamine (mono BOC form), which was the object, was 70%, By-product N, N'-di-t-butyloxycarbonyl-N, N '
-The reaction yield of dimethylethylenediamine (diBOC form) was 30%.
【０００９】（比較例１〜３）実施例１のジ−ｔ−ブチ
ルジカーボネートの滴下中のｐＨ値を表−１に示すよう
に変更し、その他は実施例１と同様に反応を行った。結
果を表−１に示した。(Comparative Examples 1 to 3) The pH value during the dropping of di-t-butyl dicarbonate of Example 1 was changed as shown in Table 1, and the other reaction was carried out in the same manner as in Example 1. . The results are shown in Table-1.
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 池平 秀行 大阪府高槻市塚原２丁目10番１号 住友 化学工業株式会社内 (72)発明者 南井 正好 大阪府高槻市塚原２丁目10番１号 住友 化学工業株式会社内 (56)参考文献 特開 昭52−73831（ＪＰ，Ａ) 特開 昭62−61957（ＪＰ，Ａ) 特開 昭64−26547（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 269/04 C07C 269/00 C07C 271/20 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideyuki Ikehira 2-10-1, Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Co., Ltd. (72) Inventor Masayoshi Minai 2--10-1, Tsukahara, Takatsuki, Osaka Sumitomo Chemical Industry Co., Ltd. (56) Reference JP-A 52-73831 (JP, A) JP-A 62-61957 (JP, A) JP-A 64-26547 (JP, A) (58) Fields investigated ( Int.Cl. 7 , DB name) C07C 269/04 C07C 269/00 C07C 271/20
Claims (2)
ｎは、１〜３の整数を示す。）で示されるアルキレンジ
アミンに酸を作用させ、次いでジ−ｔ−ブチルジカーボ
ネートをｐＨ４〜８の範囲で反応させることを特徴とす
る一般式〔２〕 （式中、Ｒおよびｎは、前記と同じ意味を表わす。）で
示されるＮ−モノ−ｔ−ブチルオキシカルボニルアルキ
レンジアミンの製造法。1. A water-hydrophilic solvent system of the general formula [1] (In the formula, R represents a hydrogen atom or a lower alkyl group,
n shows the integer of 1-3. ), An acid is allowed to act on the alkylenediamine, and then di-t-butyldicarbonate is reacted in a pH range of 4 to 8 [2]. (In the formula, R and n have the same meanings as described above.) A method for producing N-mono-t-butyloxycarbonylalkylenediamine.
製造法。2. The method according to claim 1, wherein the pH is in the range of 5 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19938594A JP3503993B2 (en) | 1994-08-24 | 1994-08-24 | Method for producing N-mono-t-butyloxycarbonylalkylenediamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19938594A JP3503993B2 (en) | 1994-08-24 | 1994-08-24 | Method for producing N-mono-t-butyloxycarbonylalkylenediamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0859594A JPH0859594A (en) | 1996-03-05 |
| JP3503993B2 true JP3503993B2 (en) | 2004-03-08 |
Family
ID=16406894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19938594A Expired - Fee Related JP3503993B2 (en) | 1994-08-24 | 1994-08-24 | Method for producing N-mono-t-butyloxycarbonylalkylenediamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3503993B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA976421B (en) * | 1996-07-22 | 1998-01-22 | Boehringer Mannheim Italia | New bis-platinum complexes with polyamine ligands as antitumor agents. |
-
1994
- 1994-08-24 JP JP19938594A patent/JP3503993B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0859594A (en) | 1996-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3503993B2 (en) | Method for producing N-mono-t-butyloxycarbonylalkylenediamine | |
| JPH029017B2 (en) | ||
| JP3769192B2 (en) | Process for producing 2- (N-phenylamino) benzoic acid | |
| KR100362706B1 (en) | A method for reducing nitro group to amine group using indium | |
| JPH078855B2 (en) | Sulfonium compound | |
| JPH0615514B2 (en) | Method for N, ω trifluoroacetylation of saturated aliphatic α, ω-diaminomonocarboxylic acid | |
| JPS61130299A (en) | Production of 5-fluorocytidine compound hydrochloride | |
| JP3503994B2 (en) | Method for purifying N-mono-t-butyloxycarbonylalkylenediamine | |
| KR100234626B1 (en) | Process for the preparation of 2-((2,6-dichlorophenyl)amino)phenylacetoxy acetic acid | |
| JPH0717935A (en) | Production of 3-aminopropionitrile | |
| JPS6316396B2 (en) | ||
| JPH09188662A (en) | Production of sulfonic acid amide compound | |
| JPH1059910A (en) | Production of aminodicarboxylic acid-n,n-diacetic acid salts | |
| JPH03181458A (en) | Production of oxiracetam | |
| EP0138156B1 (en) | Process for producing a halogen-containing ethylbenzene derivative | |
| JPH11315054A (en) | Production of aluminum compound salt | |
| JP3443584B2 (en) | Method for producing N-tert-butylpyrazinecarboxamides | |
| JPS6038396A (en) | Preparation of 5-fluorocytidine compound | |
| JP3054704B1 (en) | Deprotection method of amino group and hydroxyl group protected by alkynylmethyloxycarbonyl group | |
| JPH0952855A (en) | Production of 9-fluorenylmethanols | |
| JP2999920B2 (en) | Process for producing isonitrosoacetanilides | |
| KR960010100B1 (en) | Process for the preparation of 2-methyldithiocarbazic acid ester | |
| JPS641472B2 (en) | ||
| JPWO2002085880A1 (en) | Method for producing nitrile compound | |
| JPH0776557A (en) | Production of quaternary ammonium compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20031202 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20031209 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071219 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081219 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081219 Year of fee payment: 5 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: R3D04 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081219 Year of fee payment: 5 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081219 Year of fee payment: 5 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081219 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091219 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091219 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101219 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111219 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111219 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121219 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121219 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131219 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |