JPS5915899B2 - Production method of propargylamine - Google Patents
Production method of propargylamineInfo
- Publication number
- JPS5915899B2 JPS5915899B2 JP167076A JP167076A JPS5915899B2 JP S5915899 B2 JPS5915899 B2 JP S5915899B2 JP 167076 A JP167076 A JP 167076A JP 167076 A JP167076 A JP 167076A JP S5915899 B2 JPS5915899 B2 JP S5915899B2
- Authority
- JP
- Japan
- Prior art keywords
- butyne
- propargylamine
- silver
- reactor
- methyl
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
０ 本発明は、一般式
ＨＣヨＣ−Ｃ−ＮＨ２
（式中Ｒ１およびＲ２は、同一または異なる基で水素、
アルキル基、アリール基または脂環式基であ０ る）を
有するプロパルギルアミンの合成法に係わる。DETAILED DESCRIPTION OF THE INVENTION 0 The present invention is based on the general formula HCyoC-C-NH2 (wherein R1 and R2 are the same or different groups, hydrogen,
The present invention relates to a method for synthesizing propargylamine having an alkyl group, an aryl group, or an alicyclic group.
さらに詳述すれば、本発明は、前記一般式においてＲ１
およびＲ２が水素またはアルキル基であるプロパルギル
アミンの製法に係わる。More specifically, the present invention provides R1 in the general formula
and a method for producing propargylamine in which R2 is hydrogen or an alkyl group.
５ 同一出願人に係る特開昭５１−２８４０５号には、
適当なアルコールを原料として塩素化および得られた生
成物の圧力下における液体アンモニアによるアミノ化に
よつてなる前記一般式を有するプロパルギルアミンの合
成法が開示されている。5 Japanese Patent Application Laid-open No. 51-28405 filed by the same applicant states:
A method for synthesizing propargylamine having the general formula above is disclosed, which consists of chlorination of a suitable alcohol as a starting material and amination of the resulting product with liquid ammonia under pressure.
０ 該特許願明細書によれば、ハロゲン化物ＨＣ＝Ｃ−
Ｃ（Ｒ１）（Ｒ２）Ｃ１の液体アンモニアによる求核置
換反応は比アンモニア／塩化物４■１（重量）において
、温度−１０ないし＋４０℃、１８時間で行なわれる。0 According to the patent application specification, halide HC=C-
The nucleophilic substitution reaction of C(R1)(R2)C1 with liquid ammonia is carried out at a temperature of -10 DEG to +40 DEG C. for 18 hours at a ratio of ammonia/chloride of 4:1 (by weight).
’５ 本発明者等は周期律表第１族、第■族または第■
族に属する金属またはその塩あるいは酸化物を適当な量
で添加することにより反応時間をかなり短縮できる（場
合によつては２ないし３時間）ことを見出し、本発明に
至つた。'5 The inventors have determined that the
The present inventors have discovered that the reaction time can be considerably shortened (to 2 to 3 hours in some cases) by adding an appropriate amount of a metal belonging to the above group or its salt or oxide, leading to the present invention.
本発明に従つて添加される触媒としては、中でも、銀、
鉛、アルミニウム、これらの酸化物および塩でなる群か
ら選ばれるものがあり、その添加量はハロゲン化物の重
量基準で０．０１ないし１０％である。Catalysts added according to the invention include, among others, silver,
There is one selected from the group consisting of lead, aluminum, their oxides and salts, and the amount added is from 0.01 to 10% based on the weight of the halide.
添加量の上限は限定的なものではないが、これ以上の量
の触媒によつても該反応では同じ効果しか得られない。Although there is no upper limit to the amount of catalyst added, even if the amount of catalyst is greater than this, only the same effect can be obtained in the reaction.
さらに、必要なアンモニアの量を、ハロゲン化アルキル
の重量に対する比１：１まで、あるいは化学量論量まで
低減できることを見出した。Furthermore, it has been found that the amount of ammonia required can be reduced to a 1:1 ratio by weight of alkyl halide, or even to stoichiometric amounts.
以下の実施例は本発明をさらに明確に説明するためのも
のであるが、本発明はこれらに限定されない。実施例
１
１．２１の反応器に３−クロロ−３−オール−１−ブチ
ンの塩素化反応により得られた、３−クロロ−３−メチ
ル−１−ブチン含量−６４．４８％の粗生成物２００７
と金属銀１．５ｙとを充填した。The following examples are intended to explain the invention more clearly, but the invention is not limited thereto. Example
1 Crude product 2007 with a 3-chloro-3-methyl-1-butyne content of 64.48% obtained by the chlorination reaction of 3-chloro-3-ol-1-butyne in the reactor of 1.21
and 1.5y of metallic silver.
液体アンモニア４００ｙを充填するため該反応器を閉じ
適当に冷却した。ついで５０℃に加熱し、攪拌しながら
３時間維持した。ついで反応器を脱気し、生成物を取り
出し、沢過した。クロマトグラフイ分析によれば、沢液
は３−クロロ−３−メチル−１−ブチン含量が０．０５
％および３−アミノ−３−メチル−１−ブチン含量が６
４％であることを示した。The reactor was closed for charging with 400 y of liquid ammonia and cooled appropriately. It was then heated to 50°C and maintained for 3 hours with stirring. The reactor was then evacuated and the product removed and filtered. According to chromatographic analysis, the sap has a 3-chloro-3-methyl-1-butyne content of 0.05
% and 3-amino-3-methyl-1-butyne content is 6
It was shown that it was 4%.
蒸留後、後者の生成物１４０ｙが得られた（収率−６５
％）。After distillation, the latter product 140y was obtained (yield -65
%).
実施例 ２
３−クロロ−３−メチル−１−ブチン１００７および酸
化銀０．５７を容積１．２１の反応器に充填した。Example 2 100 7 of 3-chloro-3-methyl-1-butyne and 0.57 of silver oxide were charged into a reactor with a volume of 1.21.
反応器を閉じ、冷却したのち３−クロロ−３メチル−１
−ブチン中で発泡させながら液体アンモニア２００７を
添加した。After closing the reactor and cooling, 3-chloro-3methyl-1
- Added liquid ammonia 2007 while foaming in butyne.
反応器を２０℃に加熱し、攪拌することなく反応を６時
間続けた。The reactor was heated to 20° C. and the reaction continued for 6 hours without stirring.
ついで残つたアンモニアを大気に脱気し、反応生成物を
取り出した。The remaining ammonia was then degassed to the atmosphere and the reaction product was taken out.
反応生成物は一部液状であつた。ついで生成物を沢過し
、（圧力８０ないし８５７１ｔｍＨｇおよび温度２２な
いし２３℃で行なつた）蒸留により沢液から３−メチル
−３−アミノ１−ブチン５４７が得られた（収率＝６７
％）。塩化アンモニウムの収率は１００％（５２７）で
あつた。実施例 ３
３−クロロ−３−メチル−１−ブチン１００７および硝
酸銀０．３７を容積１．２１の反応器に充填した。The reaction product was partially liquid. The product was then filtered and distillation (carried out at a pressure of 80-8571 tmHg and a temperature of 22-23°C) gave 3-methyl-3-amino-1-butyne 547 from the sap (yield = 67
%). The yield of ammonium chloride was 100% (527). Example 3 100 7 of 3-chloro-3-methyl-1-butyne and 0.37 of silver nitrate were charged into a reactor with a volume of 1.21.
反応器を冷却し、液体アンモニア２００７をすでに充填
した原料中で発泡させながら加えた。The reactor was cooled and liquid ammonia 2007 was added while bubbling into the already charged feed.
反応器を３５℃に加熱し、攪拌することなく反応を６時
間続けた。その後、残つたアンモニアを脱気し、白色固
体状の生成物を取出した。The reactor was heated to 35° C. and the reaction continued for 6 hours without stirring. Thereafter, the remaining ammonia was degassed and a white solid product was taken out.
反応生成物を水浴中で加熱し（浴の温度４５ないし５０
℃）、生成したアミンを減圧下蒸発させ、ついで適当な
冷却トラツプで凝縮させた。The reaction product was heated in a water bath (bath temperature 45-50
C), the amine formed was evaporated under reduced pressure and then condensed in a suitable cooling trap.
得られたアミン（５３７）は高純度であつた。The obtained amine (537) was highly pure.
収率は６６％であり、塩化アンモニウムの収率は１００
％であつた。実施例 ４
３−クロロ−３−メチル−１−ブチン２５ｙおよび硝酸
鉛２．５７を容積３００ＣＣの反応器中に充填した。The yield is 66% and the yield of ammonium chloride is 100%.
It was %. Example 4 25y of 3-chloro-3-methyl-1-butyne and 2.57y of lead nitrate were charged into a reactor with a volume of 300 cc.
冷却後、液体アンモニア１００７を加えた。After cooling, liquid ammonia 1007 was added.
反応器を閉じ、ついで攪拌することなく温度３０℃の恒
温槽に１６時間入れた。その後、残つたアンモニアを脱
気し、灰色ペースト状の反応生成物を取出した。The reactor was closed and then placed in a constant temperature bath at 30° C. for 16 hours without stirring. Thereafter, the remaining ammonia was degassed, and a gray paste-like reaction product was taken out.
沢過し、減圧下（８０ないし８５ｍＴＩＬＨｇ）蒸留し
たのち、３−アミノ−３−メチル−１−ブチン１２．１
７が得られた（収率−６２％）実施例 ５
３−メチル−３−オール−１−ブチンの塩素化による、
３−メチル−３−クロロ−１−ブチン含量が６５．５８
％である粗生成物２００７を容積１．２１の反応器に充
填した。After filtering and distilling under reduced pressure (80 to 85 mTILHg), 12.1% of 3-amino-3-methyl-1-butyne was obtained.
7 was obtained (yield -62%) Example 5 By chlorination of 3-methyl-3-ol-1-butyne,
3-methyl-3-chloro-1-butyne content is 65.58
% crude product 2007 was charged into a reactor with a volume of 1.21.
さらに金属アルミニウム１５７を加えた。Furthermore, metallic aluminum 157 was added.
反応器を閉じ、冷却後、液体アンモニア４００７を充填
した。反応器の温度を３０℃に上げ、反応混合物を攪拌
しながら４時間維持した。The reactor was closed and, after cooling, filled with liquid ammonia 4007. The reactor temperature was raised to 30° C. and the reaction mixture was maintained with stirring for 4 hours.
ついでアンモニアを大気に脱気し、液体および固形塩化
アンモニウムの２相混合物でなる粗反応生成物を排出し
た。The ammonia was then degassed to the atmosphere and the crude reaction product consisting of a two-phase mixture of liquid and solid ammonium chloride was discharged.
生成物を沢過し、ついで沢液を蒸留したところ（圧力８
０ないし８５ｍｍＨｇ、温度２２ないし２３℃）、３−
アミノ−３−メチル−１−ブチン１６２７が得られた（
収率７０％）。The product was filtered and the distilled liquid was distilled (at a pressure of 8
0 to 85 mmHg, temperature 22 to 23°C), 3-
Amino-3-methyl-1-butyne 1627 was obtained (
yield 70%).
Claims (1)
水素またはアルキル基である）で表わされるプロパルギ
ルアミンの製法において、相当するプロパルギルアルコ
ールを塩素化し、得られた塩素化誘導体を、銀、鉛、ア
ルミニウム、これらの酸化物および塩でなる群から選ば
れる触媒の存在下、液体アンモニアでアミノ化すること
を特徴とする、プロパルギルアミンの製法。 ２ 前記触媒が銀、酸化銀、硝酸銀、硝酸鉛またはアル
ミニウムである特許請求の範囲第１項記載の製法。 ３ 前記プロパルギンアミンが３−アミノ−３−メチル
−１−ブチンである特許請求の範囲第１項記載の製法。[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are the same or different,
In the process for producing propargylamine represented by hydrogen or an alkyl group, the corresponding propargyl alcohol is chlorinated and the resulting chlorinated derivative is selected from the group consisting of silver, lead, aluminum, oxides and salts thereof. A process for producing propargylamine, which comprises amination with liquid ammonia in the presence of a catalyst. 2. The method according to claim 1, wherein the catalyst is silver, silver oxide, silver nitrate, lead nitrate, or aluminum. 3. The method according to claim 1, wherein the propargine amine is 3-amino-3-methyl-1-butyne.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT1916375A IT1028289B (en) | 1975-01-10 | 1975-01-10 | PROCESS FOR THE PREPARATION OF PROPARGYL AMINES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5195005A JPS5195005A (en) | 1976-08-20 |
| JPS5915899B2 true JPS5915899B2 (en) | 1984-04-12 |
Family
ID=11155411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP167076A Expired JPS5915899B2 (en) | 1975-01-10 | 1976-01-09 | Production method of propargylamine |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5915899B2 (en) |
| AT (1) | AT343619B (en) |
| BE (1) | BE837432A (en) |
| DE (1) | DE2600706C3 (en) |
| ES (1) | ES444445A1 (en) |
| FR (1) | FR2297205A1 (en) |
| GB (1) | GB1485917A (en) |
| IT (1) | IT1028289B (en) |
| NL (1) | NL7600227A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3937489B2 (en) * | 1996-05-31 | 2007-06-27 | 住友化学株式会社 | Method for producing propargylamine compound |
| CN103086894B (en) * | 2013-02-25 | 2014-10-01 | 武汉迪可表面技术有限公司 | Synthesis method of electroplating additive 3-methyl-3-aminobutyne |
-
1975
- 1975-01-10 IT IT1916375A patent/IT1028289B/en active
- 1975-12-31 GB GB5338975A patent/GB1485917A/en not_active Expired
-
1976
- 1976-01-08 FR FR7600335A patent/FR2297205A1/en active Granted
- 1976-01-09 DE DE19762600706 patent/DE2600706C3/en not_active Expired
- 1976-01-09 AT AT10776A patent/AT343619B/en not_active IP Right Cessation
- 1976-01-09 ES ES444445A patent/ES444445A1/en not_active Expired
- 1976-01-09 NL NL7600227A patent/NL7600227A/en not_active Application Discontinuation
- 1976-01-09 BE BE163403A patent/BE837432A/en not_active IP Right Cessation
- 1976-01-09 JP JP167076A patent/JPS5915899B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES444445A1 (en) | 1977-05-16 |
| IT1028289B (en) | 1979-01-30 |
| NL7600227A (en) | 1976-07-13 |
| DE2600706A1 (en) | 1976-07-15 |
| BE837432A (en) | 1976-07-09 |
| FR2297205B1 (en) | 1980-04-11 |
| FR2297205A1 (en) | 1976-08-06 |
| DE2600706C3 (en) | 1978-06-01 |
| GB1485917A (en) | 1977-09-14 |
| ATA10776A (en) | 1977-10-15 |
| JPS5195005A (en) | 1976-08-20 |
| AT343619B (en) | 1978-06-12 |
| DE2600706B2 (en) | 1977-10-06 |
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