JPS6319511B2 - - Google Patents
Info
- Publication number
- JPS6319511B2 JPS6319511B2 JP9873285A JP9873285A JPS6319511B2 JP S6319511 B2 JPS6319511 B2 JP S6319511B2 JP 9873285 A JP9873285 A JP 9873285A JP 9873285 A JP9873285 A JP 9873285A JP S6319511 B2 JPS6319511 B2 JP S6319511B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- present
- following formula
- triamine
- azacycloheptane
- 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
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- MPSFGRAGPXQWOM-UHFFFAOYSA-N 5-(azepan-2-yl)pentan-1-amine Chemical compound NCCCCCC1CCCCCN1 MPSFGRAGPXQWOM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 a-piperidone Chemical compound 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000911 decarboxylating effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Other In-Based Heterocyclic Compounds (AREA)
- Pyrrole Compounds (AREA)
Description
〈産業上の利用分野〉
本発明は下記式で示されるトリアミンおよび
その製造方法に関するものである。本発明化合物
は、例えば下記式で示される２−（ω−アミノ
アルキル）−１−アザシクロヘプタンを加熱する
ことにより製造できる。
本発明の目的物であるトリアミンは新規な化合
物であり、医薬、農薬その他工業薬品またはその
中間原料として、例えば、ゴム薬品（加硫調節
剤）として有用な化合物である。
〈従来の技術および発明が解決しようとする問題
点〉
従来、同一分子内に二級アミノ基を有する一級
アミンを分子間脱アンモニア縮合反応せしめて二
量体を製造する方法は知られていない。
〈問題点を解決するための手段および作用〉
本発明者らは新規化合物を提供すること、およ
び工業的にも入手容易な原料から製造できる化合
物を出発原料とする、新規化合物の一般的合成法
を提供することを目的に種々検討した結果、本発
明に到達した。
すなわち、本発明は下記式で示されるトリア
ミンであり、さらに下記式で示される２−（ω
−アミノアルキル）−１−アザシクロヘプタン
（ｍは３，４，５の整数）を加熱して分子間縮合
反応させることによつてトリアミンを取得するも
のである。
本発明の出発原料である２−（ω−アミノアル
キル）−１−アザシクロヘプタンは工業的に入手
容易なａ−ピロリドン、ａ−ピペリドンあるいは
ε−カプロラクタムを脱炭酸縮合反応したのち、
水素化して収率よく合成できる化合物であり、こ
の合成法は例えば特公昭41−18096号公報に記載
されている。このように、本発明の出発原料は従
来の製法に比較してはるかに合成しやすい化合物
で、技術的にも経済的にも有利である。
かくして、本発明では出発原料２−（ω−アミ
ノアルキル）−１−アザシクロヘプタンを加熱に
よつて分子間縮合反応せしめるわけである。該反
応は気相反応、液相反応のいずれも実施でき、原
料２−（ω−アミノアルキル）−１−アザシクロヘ
プタンを触媒の存在下もしくは不存在下、加熱す
ればよい。加熱温度は50〜250℃であり、反応は
数十時間内で終結する。
本発明における反応は、次式
で表わされる。
反応は不活性溶媒中で実施することもできる。
かかる不活性溶媒としては芳香族炭化水素、脂肪
族炭化水素、脂環族炭化水素、アルコール、エー
テル類などが挙げられるが、具体的にはベンゼ
ン、トルエン、キシレン、クロルベンゼン、シク
ロヘキサン、デカリンなどが挙げられる。
不活性溶媒を使用する際には、反応はその不活
性溶媒の沸点下で実施することが好ましい。
反応を促進するためには、触媒を使用するのが
好ましい。該触媒としては脱アンモニア活性ある
いは水素化活性のある化合物が用いられ、周期律
表第族金属を含む化合物、例えばラネーニツケ
ル、ラネーコバルトのようなラネー触媒、あるい
はパラジウム炭、白金黒のような貴金属触媒が好
ましい。
触媒の使用量は数％以上であればよく、種々の
反応条件から適宜決めればよい。分子間縮合反応
はアンモニアが生成し終えば終了であるので、反
応の進行にともなつて生成するアンモニアの量を
検知して、反応速度を触媒量により調整すること
ができる。
反応物から本発明化合物を分離するには、通常
の分離手段、蒸留等により行えばよい。
〈実施例〉
以下、本発明を実施例によつて説明するが、本
発明はこれに限定されるものではない。
実施例 １
２−（５−アミノペンチル）−１−アザシクロヘ
プタン100ｇ（0.54モル）をラネーニツケル35ｇ
（湿潤）の存在下、キシレン330ml中で窒素気流
下、撹拌しつつ還流加熱した。約６時間後アンモ
ニアの生成が止まつてから触媒分離、蒸留によつ
て110〜114℃（19mmHg）の留分32.5ｇおよび残
留分58.2ｇを得た。
残留分は分子量351（マススペクトル）、元素分
析値（Ｃ；74.1％、Ｈ；12.8％、Ｎ；1.16％）お
よび赤外吸収スペクトル、NMRスペクトルか
ら、ビス〔５−（２−パ−ヒドロアゼピニル）ペ
ンチル〕アミンであることを確認した。
実施例 ２〜６
２−（５−アミノペンチル）−１−アザシクロヘ
プタンとラネーニツケルおよびキシレンの比率を
変えて実施例１と同様の反応を行なつた結果を第
１表に示す。第１表中、反応率および収率は反応
混合液のガスクロ分析によつた値である。
<Industrial Application Field> The present invention relates to a triamine represented by the following formula and a method for producing the same. The compound of the present invention can be produced, for example, by heating 2-(ω-aminoalkyl)-1-azacycloheptane represented by the following formula. Triamine, which is the object of the present invention, is a novel compound and is a compound useful as a pharmaceutical, agricultural chemical, other industrial chemical, or an intermediate raw material thereof, such as a rubber chemical (vulcanization regulator). <Prior Art and Problems to be Solved by the Invention> Conventionally, there is no known method for producing a dimer by subjecting a primary amine having a secondary amino group in the same molecule to an intermolecular deammonia condensation reaction. <Means and effects for solving the problems> The present inventors provide a new compound, and a general method for synthesizing the new compound using as a starting material a compound that can be manufactured from industrially easily available raw materials. As a result of various studies aimed at providing the following, we have arrived at the present invention. That is, the present invention is a triamine represented by the following formula, and furthermore, a triamine represented by the following formula: 2-(ω
Triamine is obtained by heating and intermolecular condensation reaction of -aminoalkyl)-1-azacycloheptane (m is an integer of 3, 4, or 5). The starting material of the present invention, 2-(ω-aminoalkyl)-1-azacycloheptane, is obtained by decarboxylating and condensing a-pyrrolidone, a-piperidone, or ε-caprolactam, which are easily available industrially.
It is a compound that can be synthesized in good yield by hydrogenation, and this synthesis method is described, for example, in Japanese Patent Publication No. 18096/1983. As described above, the starting material of the present invention is a compound that is much easier to synthesize than conventional production methods, and is advantageous both technically and economically. Thus, in the present invention, the starting material 2-(ω-aminoalkyl)-1-azacycloheptane is subjected to an intermolecular condensation reaction by heating. The reaction can be carried out in either a gas phase or a liquid phase, and the raw material 2-(ω-aminoalkyl)-1-azacycloheptane may be heated in the presence or absence of a catalyst. The heating temperature is 50 to 250°C, and the reaction is completed within several tens of hours. The reaction in the present invention is expressed by the following formula: It is expressed as The reaction can also be carried out in an inert solvent.
Examples of such inert solvents include aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols, and ethers, and specific examples include benzene, toluene, xylene, chlorobenzene, cyclohexane, and decalin. Can be mentioned. When using an inert solvent, the reaction is preferably carried out below the boiling point of the inert solvent. In order to accelerate the reaction, it is preferred to use a catalyst. The catalyst used is a compound with deammonization activity or hydrogenation activity, such as a compound containing a group metal of the periodic table, such as a Raney catalyst such as Raney nickel or Raney cobalt, or a noble metal catalyst such as palladium charcoal or platinum black. is preferred. The amount of the catalyst used may be several percent or more, and may be determined as appropriate based on various reaction conditions. Since the intermolecular condensation reaction ends when ammonia is produced, the reaction rate can be adjusted by adjusting the amount of catalyst by detecting the amount of ammonia produced as the reaction progresses. The compound of the present invention can be separated from the reactant by conventional separation means such as distillation. <Examples> The present invention will be described below with reference to Examples, but the present invention is not limited thereto. Example 1 100 g (0.54 mol) of 2-(5-aminopentyl)-1-azacycloheptane was mixed with 35 g of Raney nickel.
The mixture was heated under reflux in 330 ml of xylene under a nitrogen stream with stirring in the presence of (humidity). After about 6 hours, when the production of ammonia stopped, the catalyst was separated and distilled to obtain 32.5 g of a fraction at 110-114°C (19 mmHg) and 58.2 g of a residue. The residue was found to be bis[5-(2-perhydroazepinyl)] based on the molecular weight 351 (mass spectrum), elemental analysis values (C: 74.1%, H: 12.8%, N: 1.16%), infrared absorption spectrum, and NMR spectrum. It was confirmed that it was [pentyl]amine. Examples 2 to 6 Table 1 shows the results of the same reaction as in Example 1, with different ratios of 2-(5-aminopentyl)-1-azacycloheptane, Raney nickel, and xylene. In Table 1, the reaction rate and yield are values determined by gas chromatography analysis of the reaction mixture.
【表】
実施例 ７〜８
２−（５−アミノペンチル）−１−アザシクロヘ
プタンに対してキシレン中の金属触媒の種類を変
えて実施例１と同様に反応したときの結果を第２
表に示す。[Table] Examples 7 to 8 2-(5-aminopentyl)-1-azacycloheptane was reacted in the same manner as in Example 1 by changing the type of metal catalyst in xylene.
Shown in the table.
【表】
〈発明の効果〉
本発明によれば、新規なトリアミンを提供する
ことが可能となり、かつ技術的にも経済的にも有
利な方法によつて製造することができる。[Table] <Effects of the Invention> According to the present invention, it is possible to provide a novel triamine, and it can be produced by a technically and economically advantageous method.
Claims (1)
ル）−１−アザシクロヘプタンを加熱して分子間
縮合反応を行わせることを特徴とする下記式で
示されるトリアミンの製造方法。 ３ 触媒として周期律表第族金属の少なくとも
一種を含む金属触媒を使用することを特徴とす
る、特許請求範囲第２項記載のトリアミンの製造
方法。[Claims] 1. A triamine represented by the following formula. 2. A method for producing a triamine represented by the following formula, which comprises heating 2-(ω-aminoalkyl)-1-azacycloheptane represented by the following formula to cause an intermolecular condensation reaction. 3. The method for producing triamine according to claim 2, characterized in that a metal catalyst containing at least one metal of Group Group of the Periodic Table is used as a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9873285A JPS6117559A (en) | 1985-05-09 | 1985-05-09 | Triamine and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9873285A JPS6117559A (en) | 1985-05-09 | 1985-05-09 | Triamine and its preparation |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55154663A Division JPS5780383A (en) | 1980-11-05 | 1980-11-05 | Preparation of 1-azabicyclo(m.n.0)alkane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6117559A JPS6117559A (en) | 1986-01-25 |
| JPS6319511B2 true JPS6319511B2 (en) | 1988-04-22 |
Family
ID=14227686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9873285A Granted JPS6117559A (en) | 1985-05-09 | 1985-05-09 | Triamine and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6117559A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8714806B2 (en) | 2006-07-27 | 2014-05-06 | Kobe Steel, Ltd. | Coupling apparatus and kneading equipment having kneading apparatus and drive apparatus coupled together through the coupling apparatus |
-
1985
- 1985-05-09 JP JP9873285A patent/JPS6117559A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6117559A (en) | 1986-01-25 |
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