JPH02180854A - Production of n,n-diisopropylethylamine - Google Patents
Production of n,n-diisopropylethylamineInfo
- Publication number
- JPH02180854A JPH02180854A JP63333974A JP33397488A JPH02180854A JP H02180854 A JPH02180854 A JP H02180854A JP 63333974 A JP63333974 A JP 63333974A JP 33397488 A JP33397488 A JP 33397488A JP H02180854 A JPH02180854 A JP H02180854A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acetaldehyde
- ethylamine
- catalyst
- acetone
- 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.)
- Granted
Links
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 48
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims abstract description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 16
- 229940043279 diisopropylamine Drugs 0.000 claims abstract description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract 4
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003863 metallic catalyst Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 12
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 12
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WVTKVZAXIUPMNX-UHFFFAOYSA-N 2-methylimidazo[1,2-b]pyridazine-3-carboxylic acid Chemical compound C1=CC=NN2C(C(O)=O)=C(C)N=C21 WVTKVZAXIUPMNX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 108010037444 diisopropylglutathione ester Proteins 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- HXYVTAGFYLMHSO-UHFFFAOYSA-N palmitoyl ethanolamide Chemical compound CCCCCCCCCCCCCCCC(=O)NCCO HXYVTAGFYLMHSO-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、Ｎ、Ｎ−ジイソプロピルエチルアミン（以下
、ＤＩＰＥＡという）を′５１造する方法に関し、詳し
くはエチルアミンとアセトンを出発原料とし、貴金属触
媒存在下での接触還元反応によるＤＩ））ＥＡの製造法
、及びジイソプロピルアミン（以下、ＤＩＰＡという）
とアセトアルデヒドを出発原料とし、１！１金属触媒存
在下アセトアルデヒドを反応系内に供給しながら接触還
元反応を行なうことによるＤＩＰＥＡの製造法に関する
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing N,N-diisopropylethylamine (hereinafter referred to as DIPEA) using ethylamine and acetone as starting materials and a noble metal catalyst. DI)) Method for producing EA by catalytic reduction reaction in the presence of diisopropylamine (hereinafter referred to as DIPA)
The present invention relates to a method for producing DIPEA by using acetaldehyde and acetaldehyde as starting materials and carrying out a catalytic reduction reaction while supplying acetaldehyde into the reaction system in the presence of a 1:1 metal catalyst.
ＤＩｌ）Ｌ？、Ａは医農薬の原料として有用な化合物で
ある。DIl)L? , A are compounds useful as raw materials for pharmaceuticals and agricultural chemicals.
（従来技術及び発明が解決しようとする課題）従来、Ｄ
ＩＰＥＡの！２造法としてはＤＩＰＡをジエチル硫酸で
エチル化する方法が知られている（ ＣｈｅＩＩｌ、
Ｂｅｒ、 、 ９１．３Ｈ〜３９２ （１９５８１）、
この方法によると反応器に原料のＤＩＰＡと目的物であ
るＤＩＰＥＡを等モルずつ仕込み、ジエチル硫酸を加え
１４０℃で３．５時間反応し、収率９０％でＤｌｒ”Ｅ
Ａを得ている。しかしながら、この方法は収率が高いも
のの反応を促進させるため目的物を加えるなど工業的に
有利な方法とは言い難い。(Prior art and problems to be solved by the invention) Conventionally, D
IPEA's! As a method for producing DIPA, a method of ethylating DIPA with diethyl sulfate is known (CheIIl,
Ber, 91.3H~392 (19581),
According to this method, equimolar amounts of DIPA as a raw material and DIPEA as a target product are charged into a reactor, diethyl sulfuric acid is added, and the reaction is carried out at 140°C for 3.5 hours, resulting in a yield of 90%.
I got an A. However, although this method has a high yield, it is difficult to say that it is an industrially advantageous method because the target substance is added to promote the reaction.
また、他の製造法としてＤＩＰＡをエチルアイオダイド
でエチル化する方法（Ｊ、Ｏ，Ｃ，，１６，１９１１９
５１））があるが、収率は約５０％と低く好ましい方法
とは言い難い。In addition, as another manufacturing method, a method of ethylating DIPA with ethyl iodide (J, O, C,, 16, 19119
51)), but the yield is as low as about 50% and it cannot be said to be a preferable method.
本発明の目的は、安価に人手できる原料を用いてＤ Ｉ
ＰＥＡを良好な収率で得る方法を提供することにある
。The purpose of the present invention is to produce D I using raw materials that can be done manually at low cost.
The object of the present invention is to provide a method for obtaining PEA in good yield.
（課題を解決するための手段）
本発明の第１発明は、エチルアミンとアセトンを貴金属
触媒の存在下、接触還元反応させることを特徴とするＤ
ＩＰＥＡの製造法である。(Means for Solving the Problems) The first invention of the present invention is characterized in that ethylamine and acetone are subjected to a catalytic reduction reaction in the presence of a noble metal catalyst.
This is a method for producing IPEA.
また本発明の第２発明は、ＤＩＰＡとアセトアルデヒド
を貴金属触媒の存在下、接触還元反応させてＤＩＰＥＡ
するにあたり１反応系内にアセトアルデヒドを供給しな
がら反応することを特徴とするＤＩＰＥＡの製造法であ
る。In addition, the second invention of the present invention provides DIPEA by subjecting DIPA and acetaldehyde to a catalytic reduction reaction in the presence of a noble metal catalyst.
This method for producing DIPEA is characterized in that the reaction is carried out while supplying acetaldehyde into one reaction system.
従来本第１発明の方法は意外にも知られていない。その
理由はエチルアミンにアセトンとの接触還元によりイソ
プロピル基を導入する場合、イソプロピル、２！１個の
導入は比較的容易であるが、更にもう１個のイソプロピ
ル基の導入は、中間体であるＮ−イソプロピルエチルア
ミン（以下。Surprisingly, the method of the first invention has not been known in the past. The reason for this is that when introducing isopropyl groups into ethylamine by catalytic reduction with acetone, it is relatively easy to introduce 2!1 isopropyl groups, but it is difficult to introduce one more isopropyl group into the intermediate N -isopropylethylamine (hereinafter referred to as
ＭＩＰＥＡという）のアルキル基による立体障害により
生じるその窒素原子の活性低下によって困難であると考
えられていたものと推察される。It is presumed that this was thought to be difficult due to the reduction in activity of the nitrogen atom caused by steric hindrance by the alkyl group of MIPEA.
そこで、本発明者は、水素化触媒として極めて汎用され
ているラネーＮｉ触媒を用いてエチルアミンとアセトン
の接触還元反応を試みたが、主たる生成物はアセトンの
還元体であるイソプロピルアルコールでありＤＩＰＩＥ
Ａの生成をほとんど認めることができなかった。本発明
者は、更に検討を重ねた結果、意外にも、貴金属触媒を
用いるとＤＩＰＣへの収率が著しく向上することを見出
し本発明の第１＋７？！明を完成するに至った。Therefore, the present inventor attempted a catalytic reduction reaction of ethylamine and acetone using a Raney Ni catalyst, which is extremely widely used as a hydrogenation catalyst, but the main product was isopropyl alcohol, which is a reduced form of acetone.
Almost no formation of A could be observed. As a result of further studies, the present inventor surprisingly found that the yield to DIPC is significantly improved when a noble metal catalyst is used. ! He came to complete Ming.
本発明の第２発明のような第２級アミンとアルデヒドの
接触還元反応による第３級アミンの！＋２造においては
、一般に、オートクレーブ中に第２級アミンとアルデヒ
ドのいずれも全量を仕込み水素化触媒の存在下接触還元
反応させる方法がとられている。ところが、ジイソプロ
ピルアミンとアセトアルデヒドの接触還元反応によるＤ
Ｉ ＰＥＡの！！２造の際、かかる一般の方法では貴
金属触媒及びラネーＮｉ触媒のいずれでもアセトアルデ
ヒドが本発明の目的以外の反応を起こし、ＤＩＰＥＡの
収率は極めて低いかもしくはＤ Ｉ ＰＥＡの生成をほ
とんど認めることができない、このように、従来一般的
に行なわれている方法ではＤ Ｉ Ｉ） Ｅ Ａを収率
良く得ることができない。A tertiary amine by a catalytic reduction reaction of a secondary amine and an aldehyde as in the second invention of the present invention! In +2 manufacturing, a method is generally used in which the entire amount of both the secondary amine and aldehyde is charged into an autoclave and subjected to a catalytic reduction reaction in the presence of a hydrogenation catalyst. However, D due to the catalytic reduction reaction of diisopropylamine and acetaldehyde
I PEA's! ! In this general method, acetaldehyde causes a reaction other than the purpose of the present invention in both the noble metal catalyst and the Raney Ni catalyst, and the yield of DIPEA is extremely low or the formation of DIPEA is hardly observed. As described above, it is not possible to obtain DII) EA in a good yield by the conventionally commonly used methods.
そこで１本発明者は、鋭意研究を行なった結果、意外に
も、貴金属触媒の存在下反応系内に原料のアセトアルデ
ヒドを供給しながらＤＩＰＡとアセトアルデヒドの接触
還元反応を行なうことにより、ＤＩＰＥＡの収率が著し
く向上することを見出し本発明の第２発明を完成するに
至った。ところでラネーＮｉ触媒の存在下反応系内に原
料のアセトアルデヒドを供給しながらＤＩＰＡとアセト
アルデヒドの接触還元反応を行なっても、主たる生成物
はアセトアルデヒドの還元体であるエチルアルコールで
ありＤＩＰＩＥＡの生成をほとんど認めることができな
い。Therefore, as a result of intensive research, the present inventor unexpectedly found that the yield of DIPEA could be increased by carrying out a catalytic reduction reaction between DIPA and acetaldehyde while supplying the raw material acetaldehyde into the reaction system in the presence of a noble metal catalyst. The inventors have found that the properties are significantly improved and have completed the second invention of the present invention. By the way, even if the catalytic reduction reaction of DIPA and acetaldehyde is carried out in the presence of a Raney Ni catalyst while supplying the raw material acetaldehyde into the reaction system, the main product is ethyl alcohol, which is a reduced form of acetaldehyde, and almost no DIPIEA is produced. I can't.
本第２発明では水素化触媒として貴金属触媒を用いるこ
と及び反応系内にアセトアルデヒドを供給しながら接触
還元反応を行なうことが重要である。In the second invention, it is important to use a noble metal catalyst as the hydrogenation catalyst and to carry out the catalytic reduction reaction while supplying acetaldehyde into the reaction system.
本発明の方法に用いる貴金属触媒としては通常使用され
る水素化用貴金属触媒が挙げられ、その具体例としては
パラジウム−カーボン、ルテニウム−カーボン、ロジウ
ム−カーボン、白金−カーボンなどが挙げられる。貴金
属触媒の使用量は。The noble metal catalyst used in the method of the present invention includes commonly used noble metal catalysts for hydrogenation, and specific examples thereof include palladium-carbon, ruthenium-carbon, rhodium-carbon, platinum-carbon, and the like. What is the amount of precious metal catalyst used?
エチルアミン又はジイソプロピルアミンに対して１〜２
０％重量の範囲が反応効率、触媒効率の面から好ましい
。1-2 for ethylamine or diisopropylamine
A range of 0% by weight is preferable from the viewpoint of reaction efficiency and catalyst efficiency.
本発明の第１９！明の方法について更に説明する。No. 19 of the present invention! This method will be further explained.
アセトンの使用量は通常エチルアミンに対して２倍〜３
０倍モルで、好ましくは４〜１６倍モルと過剰に用いる
ことにより反応が好適に進行する。アセトンの使用量が
エチルアミンに対して２倍モル未満であると、ＤＩＰＥ
ＡよりもＭ Ｉ Ｐ Ｅ Ａの方の生成率が増す。The amount of acetone used is usually 2 to 3 times the amount of ethylamine.
The reaction proceeds suitably by using an excess of 0 times the mole, preferably 4 to 16 times the mole. If the amount of acetone used is less than 2 times the mole of ethylamine, DIPE
The production rate of MIPEAA is higher than that of A.
エチルアミンは水溶液として反応に供することができる
。エチルアミン水溶液としては工業的に人毛しやすい７
０％品が用いられる。Ethylamine can be subjected to the reaction as an aqueous solution. As an ethylamine aqueous solution, it is industrially easy to use human hair 7
0% product is used.
本発明の第１発明の反応は比較的低温下で生成可能なＭ
Ｉ ＰＥＡを経由してＤ Ｉ ＰＥＡを生成するもの
である０本発明の第１発明の好ましい一つの実施態様に
よれば、エチルアミン、アセトン及び貴金属触媒をオー
トクレーブに仕込み、水素を導入しながら１００〜１８
０℃好ましくは１３０〜１６０℃まで徐々に加温し、該
温度に保ちながら常圧以上好ましくは５〜６０気圧で水
素の導入を続ければよい、水素導入開始後３〜１０時間
で水素の吸収が終了し、エチルアミンはほとんど消費さ
れる。他の好ましい実施態様としては、常温〜９０℃程
度でエチルアミンとアセトンを貴金属触媒存在下で接触
還元反応させてＭＩＰＣＡを製造単離し１次いで中継さ
れたＭＩＰＥＡとアセトンを貴金属触媒存在下１００〜
１８０℃好ましくは１３０〜１６０℃で接触還元反応さ
せてＤＩＰＥＡをｇｉ造するといった２ステツプの方法
が挙げられる。The reaction of the first invention of the present invention can produce M at a relatively low temperature.
According to a preferred embodiment of the first aspect of the present invention, which produces D I PEA via I PEA, ethylamine, acetone, and a noble metal catalyst are charged into an autoclave, and 100~ 18
It is sufficient to gradually heat the temperature to 0°C, preferably 130 to 160°C, and continue introducing hydrogen at normal pressure or higher, preferably 5 to 60 atmospheres while maintaining the temperature. Hydrogen absorption occurs within 3 to 10 hours after the start of hydrogen introduction. is completed and most of the ethylamine is consumed. In another preferred embodiment, MIPCA is produced and isolated by catalytic reduction reaction of ethylamine and acetone in the presence of a noble metal catalyst at room temperature to about 90°C, and then the relayed MIPEA and acetone are reacted for catalytic reduction in the presence of a noble metal catalyst.
A two-step method may be used in which DIPEA is produced by catalytic reduction reaction at 180°C, preferably 130-160°C.
また本発明の第１発明の方法において反応液中に含まれ
るＭ Ｉ ＰＥＡは反応液から中継後、アセトンとｉｌ
ｌ金属触媒存在下で接触還元反応せしめることによりＤ
ＩＰＥＡに誘導できる。Furthermore, in the method of the first aspect of the present invention, M I PEA contained in the reaction solution is transferred from the reaction solution and then transferred to acetone and IL.
D by carrying out a catalytic reduction reaction in the presence of a metal catalyst.
Can be induced to IPEA.
つぎに、本発明の第２発明の方法について更に説明する
。Next, the method of the second aspect of the present invention will be further explained.
反応系内に供給するアセトアルデヒドは、１） Ｉ Ｐ
Ａに対して１〜２．０倍モルと理論量ないし過剰に用
いるのが好ましい。アセトアルデヒドは低沸点のため溶
媒で希釈して供給する方が操作しやすい、溶媒としては
水、或はアミンとアセトアルデヒドに対して不活性な有
機溶媒などが使用できるが、後処理の操作性のよい水が
好ましい。Acetaldehyde supplied into the reaction system is 1) I P
It is preferable to use it in a theoretical amount or in excess of 1 to 2.0 times the mole of A. Because acetaldehyde has a low boiling point, it is easier to operate if it is diluted with a solvent and supplied.As a solvent, water or an organic solvent that is inert to amines and acetaldehyde can be used, but it is easier to operate in post-treatment. Water is preferred.
溶媒量としては特に制限はないが、生産効率を考慮した
場合、アセトアルデヒドに対して０．５〜３倍！ｎにが
好ましい。There is no particular limit to the amount of solvent, but considering production efficiency, it is 0.5 to 3 times the amount of acetaldehyde! n is preferred.
反応温度は通常室温〜２００℃好ましくは７０〜１５０
℃である８反応圧としては常圧以上好ましくは５〜６０
気圧である。アセトアルデヒドの供給時間は１〜６時間
で十分であり、Ｄｉ）Ａはほとんど消費される。The reaction temperature is usually room temperature to 200°C, preferably 70 to 150°C.
The reaction pressure is at least normal pressure, preferably 5 to 60°C.
It is atmospheric pressure. Acetaldehyde supply time of 1 to 6 hours is sufficient, and Di)A is almost consumed.
本発明の方法で製造されるＤ Ｉ ＰＥＡは一般的な！
１１離稍型子段１例えば反応液から濾過により触媒を除
去し、濾液を蒸留することにより極めて容易に高純度で
得られる。DI PEA produced by the method of the present invention is common!
11 Separate type substage 1 It can be obtained very easily with high purity, for example, by removing the catalyst from the reaction solution by filtration and distilling the filtrate.
本発明の方法を実施例及び比較例により説明するが１本
発明はそれらの実施例に限定されるものではない。The method of the present invention will be explained by Examples and Comparative Examples, but the present invention is not limited to these Examples.
（実施例）
実施例１
容ｆｆ１１４２の電磁式攪拌式オートクレーブに７０％
エチルアミン水溶液６４ｇ （１，０モル）、アセトン
４６４ｇ （８，０モル）及びパラジウム−カーボン６
．４ｇを仕込み、これに水素を導入、及び加熱して１６
０℃、５０気圧に昇温昇圧し接触還元反応を行なった０
次いで当該温度、当該圧を保ちながら水素の導入を続は
接触還元反応を行なった。水素吸収は水素導入開始後７
時間で終了した１反応液を冷却後、濾過して触媒を濾別
し、濾液を蒸留してＤ Ｉ ＰＥＡを８２゜８ｇ（収率
６４．２％）及びＭＩＰＩ三Ａを２０゜３ｇ（収率２３
．３％）得た。(Example) Example 1 70% in an electromagnetic stirring autoclave with a capacity of ff1142
64 g (1.0 mol) of ethylamine aqueous solution, 464 g (8.0 mol) of acetone and palladium-carbon 6
．． Charge 4g, introduce hydrogen into it, and heat to 16
The temperature and pressure were raised to 0°C and 50 atm to perform a catalytic reduction reaction.
Next, hydrogen was introduced while maintaining the temperature and pressure, followed by a catalytic reduction reaction. Hydrogen absorption begins at 7 pm after the start of hydrogen introduction.
After cooling the reaction mixture, the catalyst was removed by filtration, and the filtrate was distilled to obtain 82.8 g of DIPEA (64.2% yield) and 20.3 g of MIPI3A (yield of 64.2%). rate 23
．． 3%) obtained.
実施例２
反応温度を１８０℃に代えた他は実施例！と同様にして
反応及び後処理を行ない、ＤＩＰＥＡを５７．７ｇ （
収率４４．７％）及びＭＩＰＣＡを２９．６ｇ （収率
３４．０％）得た。Example 2 Same as Example except that the reaction temperature was changed to 180°C! The reaction and post-treatment were carried out in the same manner as above, and 57.7 g of DIPEA (
29.6 g (yield: 44.7%) and MIPCA (yield: 34.0%) were obtained.
実施例３
７０％エチルアミン水溶液を４５ｇ （０，７−ｆ−ル
）及びアセトンを４８７ｇ （８，４モル）に代えた他
は実施例１と同様にして反応及び後処理を行ない、ＤＩ
ＰＥＡを６０．８ｇ （収率６７゜：３％）及びＭＩＰ
ＣＡを１２．０ｇ （収率１９゜７％）得た。Example 3 The reaction and post-treatment were carried out in the same manner as in Example 1, except that 45 g (0,7-f-1) of 70% ethylamine aqueous solution and 487 g (8,4 mol) of acetone were used.
60.8 g of PEA (yield 67°: 3%) and MIP
12.0 g (yield 19.7%) of CA was obtained.
実施例４
７０％エチルアミン水溶液を２５７ ｇ （４−ｆｌ−
ル）、アセトンを２３２ｇ （４モル）及びパラジウム
−カーボンを３．５ｇ反応温度を７０’Ｃに代えた他は
実施例１と同様にして反応及び後処理を行ない、Ｍ Ｉ
ｒ’ Ｅ Ａを３３４．４ｇ （収率９６゜１％）得
た。なお、水素吸収は水素導入開始後４時間で終了した
。Example 4 257 g of 70% ethylamine aqueous solution (4-fl-
The reaction and post-treatment were carried out in the same manner as in Example 1, except that the reaction temperature was changed to 70'C, 232 g (4 moles) of acetone, and 3.5 g of palladium-carbon.
334.4 g (yield 96.1%) of r' EA was obtained. Note that hydrogen absorption was completed 4 hours after the start of hydrogen introduction.
ついで、得られたＭＩＰＩ三Ａ１００ｇ （１゜１５モ
ル）、アセトン３３３ｇ （５，７５モル）及びパラジ
ウム−カーボン７．４ｇを容１ｉ１Ｊｌｔの電磁式攪拌
式オートクレーブに仕込み、これに水素を導入しながら
１６０℃、４０気圧で５時間接触還元反応を行なった。Next, 100 g (1°15 mol) of the obtained MIPI3A, 333 g (5.75 mol) of acetone, and 7.4 g of palladium-carbon were charged into a 111 Jlt electromagnetic stirring autoclave, and heated to 160 g while introducing hydrogen into the autoclave. A catalytic reduction reaction was carried out at 40 atm at 0.degree. C. for 5 hours.
反応液を冷却後、濾過して触媒を濾別し、濾液を蒸留し
てＤＩＰＥＡを１０５．９ｇ （収率７１．４％）、未
反応Ｍ Ｉ ＰＥＡを８．４ｇ（回収率８，４％）得た
。After the reaction solution was cooled, it was filtered to remove the catalyst, and the filtrate was distilled to obtain 105.9 g of DIPEA (yield 71.4%) and 8.4 g of unreacted MI PEA (recovery rate 8.4%). )Obtained.
実施例５
容ｆｆ１ｌＪ２の電磁式攪拌式オートクレーブにＤＩＩ
’Ａ２０２ｇ （２，０モル）及びパラジウム−カーボ
ン１２．９ｇを仕込み、これに水素を導入し加熱し１２
０℃、２５気圧とした８次いで５０％アセトアルデヒド
水溶液１８４ｇ （２゜１モル）を高圧定攪ポンプにて
及び２５気圧を保つように水素をオートクレーブ内に３
時間かけて供給しながら接触還元反応を行なった０反応
液を冷却後、濾過して触媒を濾別し、２層に分液した濾
液のオイル層を蒸留してＤ Ｉ Ｐ ＥＡを２１０゜Ｏ
ｇ（収率８１゜４％）及び未反応ＤＩＰＡを１７．８ｇ
（回収率８．８％）得た。他にエタノールがＩＱ、４
ｇ （収率１０．８％）副生していた。Example 5 DII was placed in an electromagnetic stirring autoclave with a capacity of ff1lJ2.
202 g (2.0 mol) of 'A and 12.9 g of palladium-carbon were charged, hydrogen was introduced into the mixture, and the mixture was heated to 12.0 g.
8 Then, 184 g (2° 1 mol) of a 50% acetaldehyde aqueous solution was added to the autoclave at 0°C and 25 atm using a high-pressure constant stirring pump, and hydrogen was added to the autoclave to maintain the pressure at 25 atm.
The catalytic reduction reaction was carried out while being fed over a period of time. After cooling, the reaction solution was filtered to remove the catalyst. The oil layer of the filtrate was separated into two layers and distilled to produce DIP EA at 210°O.
g (yield 81°4%) and 17.8 g of unreacted DIPA
(Recovery rate: 8.8%). Besides, ethanol has an IQ of 4
g (yield 10.8%) was produced as a by-product.
実施例６
パラジウム−カーボンを７．７ｇ及び５０％アセトアル
デヒド水ｉ８液を２２８ｇ （２，６モル）に代えた他
は実施例５と同様にして反応及び後処理を行ない、Ｄ
Ｉ ）） ［’：八を２３６．１ｇ （収率９１．５％
）得、未反応ＤＩＰＡは０．６ｇ （回収率Ｑ、３％）
とほとんど残っていなかった。他にエタノールが１０．
５ｇ （収率８．８％）副生じていた。Example 6 The reaction and post-treatment were carried out in the same manner as in Example 5, except that 7.7 g of palladium-carbon and 228 g (2.6 mol) of 50% aqueous acetaldehyde solution I8 were used.
I)) [': 236.1g of 8 (yield 91.5%
), unreacted DIPA was 0.6 g (recovery rate Q, 3%)
There wasn't much left. In addition, ethanol is 10.
5g (yield: 8.8%) was produced as a by-product.
比較例１
容量１℃の電磁式攪拌式オートクレーブに１）ＩＰΔ２
０２ｇ （２，０モル）、５０％アセトアルデヒド水溶
液１８４ｇ（２，１モル）及びパラジウム−カーボン７
．７ｇを仕込み、これに水素を導入しながら１２０℃、
２５気圧で接触還元反応を行なったところ、１時間３０
分で水素の吸収が止まり反応は終丁した。反応液を冷却
後、濾過して触媒を濾別し、２層に分液した濾液のオイ
ル層を蒸留してＤ Ｉ ＰＥＡを２３．５ｇ （収率９
．１％）及び未反応ＤＩＰＡを６８．３ｇ （回収率３
３．８％）得た。他に高沸物が多種多量に副生じていた
。Comparative Example 1 1) IPΔ2 in an electromagnetic stirring autoclave with a capacity of 1°C
02 g (2.0 mol), 184 g (2.1 mol) of 50% aqueous acetaldehyde solution and palladium-carbon 7
．． 7g was charged and heated to 120℃ while introducing hydrogen into it.
When the catalytic reduction reaction was carried out at 25 atmospheres, it took 30 minutes for 1 hour.
After a few minutes, hydrogen absorption stopped and the reaction came to an end. After cooling the reaction solution, it was filtered to remove the catalyst, and the oil layer of the filtrate separated into two layers was distilled to obtain 23.5 g of D I PEA (yield: 9).
．． 1%) and 68.3 g of unreacted DIPA (recovery rate 3
3.8%) was obtained. Many other high-boiling substances were produced as by-products.
比較例２
パラジウム−カーボンをラネーＮｉ５２ｇに代えた他は
実施例６と同様にして反応及び後処理を行なった。ＤＩ
ＰＥＡの生成量はトレースであり、未反応ＤＩＰＡを１
９４．９ｇ （回収率９６．５％）及びエタノールをｚ
ｓｇ（収率９８．７％）得た。Comparative Example 2 The reaction and post-treatment were carried out in the same manner as in Example 6, except that 52 g of Raney Ni was used instead of palladium-carbon. D.I.
The amount of PEA produced is a trace, and the amount of unreacted DIPA is 1
94.9g (recovery rate 96.5%) and ethanol
sg (yield 98.7%) was obtained.
（発明の効果）
本発明の第１及び２発明によれば、従来法に比べ安価な
原料で良好な収率でＤ Ｉ Ｐ ｒＥ Ａが得られる。(Effects of the Invention) According to the first and second aspects of the present invention, D I P rE A can be obtained in good yield using cheaper raw materials than in conventional methods.
特許出願人 広栄化字工業株式会社Patent applicant Koeikaji Industrial Co., Ltd.
Claims (1)
触還元反応させることを特徴とするＮ，Ｎ−ジイソプロ
ピルエチルアミンの製造法。 ２）ジイソプロピルアミンとアセトアルデヒドを貴金属
触媒の存在下、接触還元反応させてＮ，Ｎ−ジイソプロ
ピルエチルアミンするにあたり、反応系内にアセトアル
デヒドを供給しながら反応することを特徴とするＮ，Ｎ
−ジイソプロピルエチルアミンの製造法。[Claims] 1) A method for producing N,N-diisopropylethylamine, which comprises subjecting ethylamine and acetone to a catalytic reduction reaction in the presence of a noble metal catalyst. 2) N,N, which is characterized in that when diisopropylamine and acetaldehyde are subjected to a catalytic reduction reaction to form N,N-diisopropylethylamine in the presence of a noble metal catalyst, the reaction is carried out while supplying acetaldehyde into the reaction system.
-Production method of diisopropylethylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63333974A JP2740828B2 (en) | 1988-12-29 | 1988-12-29 | Method for producing N, N-diisopropylethylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63333974A JP2740828B2 (en) | 1988-12-29 | 1988-12-29 | Method for producing N, N-diisopropylethylamine |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9260814A Division JP2851274B2 (en) | 1997-09-08 | 1997-09-08 | Method for producing N, N-diisopropylethylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02180854A true JPH02180854A (en) | 1990-07-13 |
| JP2740828B2 JP2740828B2 (en) | 1998-04-15 |
Family
ID=18272073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63333974A Expired - Fee Related JP2740828B2 (en) | 1988-12-29 | 1988-12-29 | Method for producing N, N-diisopropylethylamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2740828B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1020424A1 (en) * | 1999-01-14 | 2000-07-19 | Basf Aktiengesellschaft | Method for the production of N-Ethyl-diisopropylamin |
| US6834939B2 (en) | 2002-11-23 | 2004-12-28 | Silverbrook Research Pty Ltd | Micro-electromechanical device that incorporates covering formations for actuators of the device |
| WO2007137990A1 (en) * | 2006-05-31 | 2007-12-06 | Basf Se | Process for the preparation of an amine |
| US9416689B2 (en) | 2012-12-28 | 2016-08-16 | Nittan Valve Co., Ltd. | Method and apparatus for controlling a phase varying apparatus |
| US9884805B2 (en) | 2014-02-18 | 2018-02-06 | Basf Antwerpen Nv | Method for producing N-ethyl-diisopropylamine |
-
1988
- 1988-12-29 JP JP63333974A patent/JP2740828B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1020424A1 (en) * | 1999-01-14 | 2000-07-19 | Basf Aktiengesellschaft | Method for the production of N-Ethyl-diisopropylamin |
| US6111141A (en) * | 1999-01-14 | 2000-08-29 | Basf Aktiengesellschaft | Preparation of N-ethyldiisopropylamine |
| US6834939B2 (en) | 2002-11-23 | 2004-12-28 | Silverbrook Research Pty Ltd | Micro-electromechanical device that incorporates covering formations for actuators of the device |
| WO2007137990A1 (en) * | 2006-05-31 | 2007-12-06 | Basf Se | Process for the preparation of an amine |
| US8034978B2 (en) | 2006-05-31 | 2011-10-11 | Basf Se | Process for the preparation of an amine |
| US9416689B2 (en) | 2012-12-28 | 2016-08-16 | Nittan Valve Co., Ltd. | Method and apparatus for controlling a phase varying apparatus |
| US9884805B2 (en) | 2014-02-18 | 2018-02-06 | Basf Antwerpen Nv | Method for producing N-ethyl-diisopropylamine |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2740828B2 (en) | 1998-04-15 |
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