JPS625898B2 - - Google Patents
Info
- Publication number
- JPS625898B2 JPS625898B2 JP58212860A JP21286083A JPS625898B2 JP S625898 B2 JPS625898 B2 JP S625898B2 JP 58212860 A JP58212860 A JP 58212860A JP 21286083 A JP21286083 A JP 21286083A JP S625898 B2 JPS625898 B2 JP S625898B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- primary amine
- hydrogen
- reaction
- alkyl
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 150000003141 primary amines Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 7
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N methyl alpha-methylvinyl ketone Natural products CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 7
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 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
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- -1 dioxane Chemical compound 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- FQBQBRBAJDVVOH-UHFFFAOYSA-N n-ethyl-3-methylbutan-2-amine Chemical compound CCNC(C)C(C)C FQBQBRBAJDVVOH-UHFFFAOYSA-N 0.000 description 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は一般式（）
（式中、Ｒは炭素数１〜４のアルキル基を示す）
で表わされるＮ−アルキル−１・２−ジメチルプ
ロピルアミンの製造法に関する。更に詳しくはメ
チルイソプロピルケトン（以下MIPKと略す）と
一般式（）：
Ｒ−NH2 （）
（式中、Ｒは前記と同じ）
で表わされる１級アミンとをパラジウム触媒の存
在下接触水素還元せしめ一般式（）の化合物を
製造する方法に関する。[Detailed Description of the Invention] The present invention relates to the general formula () (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.) More specifically, methyl isopropyl ketone (hereinafter abbreviated as MIPK) and a primary amine represented by the general formula (): R-NH 2 () (wherein R is the same as above) were subjected to catalytic hydrogen reduction in the presence of a palladium catalyst. The present invention relates to a method for producing a compound of the general formula ().
一般式（）の化合物は医薬、農薬の原料とし
て有用である。この一般式（）の化合物の従来
知られた製造法としては２−アルキルアミノ−２
−メチルブタン−３−オールを出発原料として用
いる方法のみである〔G.Hennion著J.O.C.302650
（1965）〕。この方法によれば、出発原料を塩化水
素及び塩化チオニルで処理して水酸基を塩素に置
換し、次いで転位を伴なう脱塩酸反応を行ない得
られたＮ−アルキル−１・２−ジメチルアリルア
ミンを水素添加して一般式（）の化合物を製造
するという長い工程を経なけれがならず、工業的
に有利な製造法ではない。 The compound of general formula () is useful as a raw material for medicines and agricultural chemicals. A conventionally known method for producing the compound of general formula () is 2-alkylamino-2
- The only method using methylbutan-3-ol as a starting material [G. Hennion, JOC 30 2650
(1965)]. According to this method, the starting material is treated with hydrogen chloride and thionyl chloride to replace the hydroxyl group with chlorine, and then a dehydrochloric acid reaction accompanied by rearrangement is performed to obtain N-alkyl-1,2-dimethylallylamine. It is not an industrially advantageous production method because it requires a long process of hydrogenation to produce the compound of general formula ().
本発明者らは、一般に入手が容易であるMIPK
と一般式（）の１級アミンとを接触水素還元す
る方法を鋭意検討した結果、還元触媒として最も
汎用されるラネーニツケルやラネーコバルトを使
用した場合には、生成物は複雑な混合物であり、
目的物の一般式（）の化合物への選択率は極め
て低いものであつた。そこで、更に鋭意検討した
処、触媒としてパラジウムを用いることにより始
めて高選択的、高収率で高純度の一般式（）の
化合物が得られることを見い出し、本発明を完成
するに至つた。 The present inventors developed MIPK, which is generally easily available.
As a result of intensive investigation into a method for catalytic hydrogen reduction of and a primary amine of the general formula (), we found that when Raney nickel or Raney cobalt, which are the most widely used reduction catalysts, are used, the product is a complex mixture;
The selectivity to the target compound of general formula () was extremely low. Therefore, after further intensive study, it was discovered that the compound of the general formula () can be obtained with high selectivity, high yield, and high purity only by using palladium as a catalyst, leading to the completion of the present invention.
本発明において使用される一般式（）の１級
アミンとしては、例えばメチルアミン、エチルア
ミン、プロピルアミン、又はブチルアミンであ
り、その使用量はMIPKに対して0.8〜２倍モルの
割合である。パラジウム触媒はアルミナ、ケイソ
ウ土、白土、又は活性炭のような担体にパラジウ
ムを担持させたものである。該触媒に含有されて
いるパラジウムの量は普通0.2〜10重量％の範囲
内で選択される。該触媒はMIPKに対して0.1〜20
重量％の割合で用いられる。 The primary amine of the general formula () used in the present invention is, for example, methylamine, ethylamine, propylamine, or butylamine, and the amount used is 0.8 to 2 times the mole of MIPK. The palladium catalyst is one in which palladium is supported on a carrier such as alumina, diatomaceous earth, clay, or activated carbon. The amount of palladium contained in the catalyst is usually selected within the range from 0.2 to 10% by weight. The catalyst is 0.1-20 for MIPK
It is used in proportions of % by weight.
次いで反応条件としては、反応性は常圧以上、
好ましくは５〜100気圧の水素分圧で行なうのが
良い。反応温度は室温以上、好ましくは50〜150
℃の範囲内で行なうのが適当である。本反応には
溶媒は特に必要としないが、溶媒の存在下でも行
なうことができる。溶媒としては反応条件下で不
活性な液体が選ばれるが、その代表的なものとし
て、ｎ−ヘキサンのような飽和炭化水素、メタノ
ールのような飽和アルコール、ジオキサンのよう
な環状エーテル及び水などが挙げられる。 Next, the reaction conditions are that the reactivity is above normal pressure,
Preferably, the hydrogen partial pressure is 5 to 100 atmospheres. The reaction temperature is above room temperature, preferably 50-150℃
It is appropriate to carry out the reaction within the range of ℃. This reaction does not particularly require a solvent, but can be carried out in the presence of a solvent. A liquid that is inert under the reaction conditions is selected as the solvent, and typical examples include saturated hydrocarbons such as n-hexane, saturated alcohols such as methanol, cyclic ethers such as dioxane, and water. Can be mentioned.
本発明に従えば、１〜５時間で反応が完結し、
副反応は殆ど起らず、高収率で接触水素還元が達
成される。即ち、高純度の一般式（）の化合物
はMIPKに対して96％以上の収率で得られ、
MIPKのアルドール縮合物は実質的に生成しない
と云う極めて有利な製造法である。 According to the present invention, the reaction is completed in 1 to 5 hours,
Catalytic hydrogen reduction is achieved in high yield with almost no side reactions occurring. That is, a highly purified compound of general formula () can be obtained with a yield of 96% or more based on MIPK,
This is an extremely advantageous production method in that virtually no aldol condensate of MIPK is produced.
次に、実施例を挙げて本発明を説明する。但し
本発明はこれに限定されるものではない。 Next, the present invention will be explained by giving examples. However, the present invention is not limited to this.
実施例 １
１容量の電磁撹拌式オートクレーブに
MIPK258ｇ、70％エチルアミン水溶液193ｇ、及
び５％Pd−カーボン2.6ｇを仕込み、それに水素
を導入して圧力を20気圧にし、60℃で接触水素還
元した。反応が進行するにつれ水素圧力は減少す
るので、逐次水素を追加した。２時間で水素の吸
収はなくなり反応が終了した。得られた反応液を
ろ過して触媒を除去し、分液して、油層を蒸留し
て純度（ガスクロマトグラフイーによる、以下同
様）99.6％のＮ−エチル−１・２−ジメチルプロ
ピルアミン338ｇ（収率98.0％）を得た。Example 1 In a 1-capacity electromagnetic stirring autoclave
258 g of MIPK, 193 g of a 70% ethylamine aqueous solution, and 2.6 g of 5% Pd-carbon were charged, hydrogen was introduced thereto to make the pressure 20 atm, and catalytic hydrogen reduction was carried out at 60°C. As the reaction progressed, the hydrogen pressure decreased, so hydrogen was added sequentially. After 2 hours, hydrogen absorption stopped and the reaction was completed. The resulting reaction solution was filtered to remove the catalyst, separated, and the oil layer was distilled to obtain 338 g of N-ethyl-1,2-dimethylpropylamine with a purity of 99.6% (by gas chromatography, hereinafter the same). A yield of 98.0%) was obtained.
実施例 ２
１容量の電磁撹拌式オートクレーブに
MIPK258ｇ、40％メチルアミン水溶液233ｇ、５
％Pd−カーボン2.6ｇを仕込み、それに水素を導
入して圧力を20気圧にし、50℃で接触水素還元し
た。反応が進行するにつれ水素圧力は減少するの
で、逐次水素を追加した。1.5時間で水素の吸収
はなくなり反応が終了した。次いで実施例１と同
様に処理して純度99.5％のＮ−メチル−１・２−
ジメチルプロピルアミン293ｇ（収率96.7％）を
得た。Example 2 In a 1-capacity electromagnetic stirring autoclave
MIPK258g, 40% methylamine aqueous solution 233g, 5
% Pd-carbon was charged, hydrogen was introduced thereto to make the pressure 20 atm, and catalytic hydrogen reduction was carried out at 50°C. As the reaction progressed, the hydrogen pressure decreased, so hydrogen was added sequentially. After 1.5 hours, hydrogen absorption stopped and the reaction was completed. Next, it was treated in the same manner as in Example 1 to obtain N-methyl-1,2- with a purity of 99.5%.
293 g (yield 96.7%) of dimethylpropylamine was obtained.
Claims (1)
ロピルアミンを製造するにあたり、メチルイソプ
ロピルケトンと一般式（）： Ｒ−NH2 （） （式中、Ｒは前記と同じ） で表わされる１級アミンとをパラジウム触媒の存
在下接触水素還元することを特徴とするＮ−アル
キル−１・２−ジメチルプロピルアミンの製造
法。 ２ 一般式（）の１級アミンをメチルイソプロ
ピルケトンに対し0.8〜２倍モルの割合で用い、
50〜150℃の反応温度で接触水素還元を行なう特
許請求の範囲第１項記載の方法。 ３ 一般式（）の１級アミンがエチルアミンで
ある特許請求の範囲第１項記載の方法。[Claims] 1 General formula (): (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.) In producing N-alkyl-1,2-dimethylpropylamine represented by the following, methyl isopropyl ketone and the general formula (): R-NH 2 ( ) (wherein R is the same as above) A method for producing N-alkyl-1,2-dimethylpropylamine, which comprises subjecting a primary amine represented by the following formula to catalytic hydrogen reduction in the presence of a palladium catalyst. 2 Using the primary amine of the general formula () in a molar ratio of 0.8 to 2 times that of methyl isopropyl ketone,
The method according to claim 1, wherein the catalytic hydrogen reduction is carried out at a reaction temperature of 50 to 150°C. 3. The method according to claim 1, wherein the primary amine of general formula () is ethylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21286083A JPS60104044A (en) | 1983-11-11 | 1983-11-11 | Production of n-alkyl-1,2-dimethylpropylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21286083A JPS60104044A (en) | 1983-11-11 | 1983-11-11 | Production of n-alkyl-1,2-dimethylpropylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60104044A JPS60104044A (en) | 1985-06-08 |
| JPS625898B2 true JPS625898B2 (en) | 1987-02-07 |
Family
ID=16629499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21286083A Granted JPS60104044A (en) | 1983-11-11 | 1983-11-11 | Production of n-alkyl-1,2-dimethylpropylamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60104044A (en) |
-
1983
- 1983-11-11 JP JP21286083A patent/JPS60104044A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| SB VYS SK CHEM TECHNOL PRAZE ORG CHEM TECHNOL=1973 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60104044A (en) | 1985-06-08 |
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