JPH01165555A - Production of allyl type amine - Google Patents
Production of allyl type amineInfo
- Publication number
- JPH01165555A JPH01165555A JP62323833A JP32383387A JPH01165555A JP H01165555 A JPH01165555 A JP H01165555A JP 62323833 A JP62323833 A JP 62323833A JP 32383387 A JP32383387 A JP 32383387A JP H01165555 A JPH01165555 A JP H01165555A
- Authority
- JP
- Japan
- Prior art keywords
- allyl
- amine
- allyl alcohol
- mmol
- compound
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000001412 amines Chemical class 0.000 title abstract description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title description 2
- -1 phosphorus compound Chemical class 0.000 claims abstract description 32
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 11
- 150000003141 primary amines Chemical class 0.000 claims abstract description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 abstract description 48
- 239000003054 catalyst Substances 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 5
- 229910002666 PdCl2 Inorganic materials 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000003335 secondary amines Chemical class 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 229910021605 Palladium(II) bromide Inorganic materials 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 abstract description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 abstract 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 abstract 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 101100062772 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) dcl-2 gene Proteins 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JWAJUTZQGZBKFS-UHFFFAOYSA-N n,n-diethylprop-2-en-1-amine Chemical compound CCN(CC)CC=C JWAJUTZQGZBKFS-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KTOQRRDVVIDEAA-UHFFFAOYSA-N 2-methylpropane Chemical compound [CH2]C(C)C KTOQRRDVVIDEAA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100189618 Caenorhabditis elegans pdi-2 gene Proteins 0.000 description 1
- 101100028920 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cfp gene Proteins 0.000 description 1
- 229910021606 Palladium(II) iodide Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JFIOVJDNOJYLKP-UHFFFAOYSA-N bithionol Chemical compound OC1=C(Cl)C=C(Cl)C=C1SC1=CC(Cl)=CC(Cl)=C1O JFIOVJDNOJYLKP-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- WJYIMFNLIJXFMX-UHFFFAOYSA-N n-methyl-n-prop-2-enylaniline Chemical compound C=CCN(C)C1=CC=CC=C1 WJYIMFNLIJXFMX-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- HNNUTDROYPGBMR-UHFFFAOYSA-L palladium(ii) iodide Chemical compound [Pd+2].[I-].[I-] HNNUTDROYPGBMR-UHFFFAOYSA-L 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 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〕
本発明はアリル型アミンの製造法に関する。更に詳しく
述べるならば、本発明は、凝集剤等として有用なカチオ
ン型ポリマーや医薬および農薬の原料として広く用いら
れるアリル型アミンの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing allylic amines. More specifically, the present invention relates to a method for producing cationic polymers useful as flocculants, etc., and allylic amines widely used as raw materials for pharmaceuticals and agricultural chemicals.
塩化アリルとアンモニアを反応させることによりアリル
アミンを製造することが、今日、行われている（米国特
許２２１６５４８および３１７５００９参照）。また、
アリル型不飽和エーテルまたはアリル型不飽和アルコー
ルのカルボン酸エステルとアンモニアを、パラジウム化
合物と３価の燐化合物または砒素化合物とを組み合わせ
て触媒として用いて反応させ、アリル型アミンを製造す
ることが提案されている（特公昭４９−２０１６２参照
）。しかし、塩化アリルやアリルエステルを用いた場合
、アリルアミンの合成に伴い、塩酸またはカルボン酸が
生じる。It is currently practiced to produce allylamine by reacting allyl chloride with ammonia (see US Pat. Nos. 2,216,548 and 3,175,009). Also,
It is proposed to produce an allyl amine by reacting a carboxylic acid ester of an allyl unsaturated ether or an allyl unsaturated alcohol with ammonia using a combination of a palladium compound and a trivalent phosphorus compound or an arsenic compound as a catalyst. (Refer to Japanese Patent Publication No. 49-20162). However, when allyl chloride or allyl ester is used, hydrochloric acid or carboxylic acid is generated during the synthesis of allylamine.
そして、これらは、アンモニアまたは生成したアミンと
塩を形成するため酸は再利用できず、またアミンを回収
するためには等モルの強アルカリにて中和する必要があ
る。また塩を生じるためプロセスが複雑になるという問
題を生じる。Since these forms salts with ammonia or the produced amine, the acid cannot be reused, and in order to recover the amine, it is necessary to neutralize it with an equimolar amount of strong alkali. Moreover, since salt is produced, the process becomes complicated.
一方、アリル型アルコールを原料に用いる場合には、副
生物として水が生成し、この水はアミンと反応すること
がないので、上記の如き損失が生じないだけでなく、プ
ロセスも簡単になる。しかし、アリル型アルコールは、
塩化アリルやアリルエステルに較べ、その反応性が非常
に低い。On the other hand, when allyl alcohol is used as a raw material, water is produced as a by-product, and this water does not react with the amine, so that not only does the loss as described above not occur, but the process is also simplified. However, allylic alcohol
Its reactivity is very low compared to allyl chloride and allyl ester.
このことは、下記衣（Ｒｅｓｅａｒｃｈ Ｄｉｓｃｌｏ
ｓｕｒｅ、 Ｍａｙ１９７８．３５頁より抜粋）にみら
れるアリルアセテートとアリルアルコールの反応性の違
いにより確認される。This is explained in the Research Disclo below.
This is confirmed by the difference in reactivity between allyl acetate and allyl alcohol, which can be seen in ``Sure, May 1978, page 35''.
以下余白
同−触媒を用いているにもかかわらず、アリルアルコー
ルの場合、温度、アリル化合物と触媒のモル比および反
応時間のいずれも有利な条件下においても、収率はむし
ろ低い値である。このようにアリルアルコールの反応性
は、カルボン酸エステルに比べ圧倒的に乏しい。In the case of allyl alcohol, the yield is rather low even under favorable conditions of temperature, molar ratio of allyl compound to catalyst, and reaction time, even though the same catalyst is used. As described above, the reactivity of allyl alcohol is overwhelmingly poorer than that of carboxylic acid ester.
アリルアルコールをアリル源に用いる場合には、他にも
問題点がある。それは反応にともない、配位子であるホ
スフィンがアリルアルコールの酸素原子により酸化され
ることである。There are other problems when using allyl alcohol as an allyl source. This is because the phosphine ligand is oxidized by the oxygen atom of allyl alcohol during the reaction.
Ａｔｋｉｎｓらは、Ｐｄ（ＣＨ２ＣＯＣＨ２ＣＯＣＨ３
）ｚを出発錯体に用い、トリフェニルホスフィンをパラ
ジウムと等モル量添加した系で、アリルアルコールとジ
エチルアミンよりアリルジエチルアミンを合成している
（Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ ｆｌｈ４
３．３８２１〜３８２４頁（１９７０年）〕。しかし、
前述したように、トリフェニルホスフィンはアリルアル
コールにより徐々に酸化されるため、黒色のパラジウム
化合物の析出が認められ、活性が持続しないことが実験
により認められた。一方、多座配位リン化合物を用いる
と、触媒の安定性は飛躍的に向上し、黒色のパラジウム
化合物の析出もなく、またくり返して触媒を使用しても
ほとんど活性の低下は見られなかった。Atkins et al.
) Z is used as a starting complex, and allyl diethylamine is synthesized from allyl alcohol and diethylamine in a system in which triphenylphosphine is added in an equimolar amount to palladium (Tetrahedron Letters flh4
3.3821-3824 (1970)]. but,
As mentioned above, since triphenylphosphine is gradually oxidized by allyl alcohol, a black palladium compound was observed to be deposited, and it was found through experiments that the activity did not last. On the other hand, when a multidentate phosphorus compound was used, the stability of the catalyst was dramatically improved, there was no precipitation of black palladium compounds, and there was almost no decrease in activity even when the catalyst was used repeatedly. .
以上のようにアリルアルコールはカルボン酸エステルに
比べ、酸を副生じないので有利であるが、反応性が低く
、またアリルアルコールの構成原子である酸素原子によ
り配位子であるホスフィンが酸化される欠点がある。As mentioned above, allyl alcohol is advantageous over carboxylic acid esters because it does not produce acid as a by-product, but it also has low reactivity and the phosphine, which is a ligand, is oxidized by the oxygen atom that is a constituent atom of allyl alcohol. There are drawbacks.
本発明は、これらの欠点を解消し、実用可能な方法を提
供するものである。The present invention eliminates these drawbacks and provides a practical method.
Ｃ問題点を解決するための手段〕
本発明によれば即ちアリル型アミンの製造方法が提供さ
れるのであって、この方法は、下記式、Ｒ，Ｒ。Means for Solving Problem C] According to the present invention, there is provided a method for producing an allylic amine, which has the following formula, R, R.
＼ １
／Ｃ＝Ｃ−Ｃ１１・−０１１
〔上式中、Ｒ，、Ｒ２およびＲ１は、それぞれ独立に、
水素原子、炭素数１〜８の脂肪族炭化水素基、脂環族炭
化水素基、または芳香族炭化水素基を表す〕で示される
アリル型アルコールと第一級アミンおよび／または第二
級アミンとを、パラジウムの化合物と多座配位リン化合
物の存在下に、反応させることを特徴とする。\ 1 /C=C-C11・-011 [In the above formula, R,, R2 and R1 are each independently,
represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group] and a primary amine and/or a secondary amine. is characterized by reacting with a palladium compound and a polydentate phosphorus compound.
本発明に有用な第一級アミンの例としては、脂肪族鎖状
および環状アミン、例えば、ＣＩＩ ｓ Ｎ ＩＩ ２
。Examples of primary amines useful in the present invention include aliphatic linear and cyclic amines, such as CII s N II 2
.
Ｃ２Ｈ３ＮＨ２、Ｃｌ２ＮＨ２，ｎ Ｃ３Ｈ？ＮＨ２
、＋ｓｏ ＣＪｔＮＨｚ 。C2H3NH2, Cl2NH2,n C3H? NH2
, +so CJtNHz.
ｎ ＣｊｌＪｔ１２． ｉｓｏ ＣＪＪｔｌ□、
ｔ Ｃ４１１ＪＩＩｚ 、 ｎ−Ｃ５ＨｓＮＨｚ 、
ｎ−Ｃ３ＨＩＩＮＨ２、１ｓｏ−ＣｓＨ＋ ＩＮＨ２
、ｎ −ＣｓＨ＋ＪＩｌｚ 、 ｎ Ｃ２Ｈ３ＮＨ２
、ｃｙｃｌｏ Ｃａ１ｌ １ＮＨ２など、芳香族アミ
ン、例えば、Ｃｌ２ＮＨ２、Ｃ６Ｈ，Ｃｌ２ＮＨ２゜ｏ
−Ｃｌ１ＣＪ＜Ｎ１１２． ｍ−Ｃｌ、ＣＪ４ＮＩＬｚ
、 ｐ−Ｃｌ１ｓＣ６１１４Ｎｌｌｚ。n CjlJt12. iso CJJtl□,
tC411JIIz, n-C5HsNHz,
n-C3HIINH2, 1so-CsH+ INH2
, n -CsH+JIlz, n C2H3NH2
, cyclo Ca1l 1NH2, etc., aromatic amines such as Cl2NH2, C6H, Cl2NH2゜o
-Cl1CJ<N112. m-Cl, CJ4NILz
, p-Cl1sC6114Nllz.
０−ＣＨ３０Ｃ６Ｈ４ＮＨ２、ｍ−Ｃｌ、０ＣＪｎＮＨ
２，ｐ−ＣＨｓＯＣｓｌｌＪＨ２゜ｏ ＣＩＣ６１１
４ＮｔＪ２． ｍ ＣＩＣ５ｌＬＮＲ２，ｐ ＣＩ
Ｃ６１１ＪＪＩ２゜２ 、６−（Ｃｌ５）２Ｃ６Ｈ，Ｎ
Ｈ２，２、４、６−（ＣＨ３）、Ｃ６１１２ＮＨ２など
、および脂肪族および芳香族ジアミン、例えば、ＮＨ２
ＣＨ２ＣＨ２Ｎ１＋２． ＮＨ，ＣＨ２ＣＨ２Ｃ１１２
Ｎ１１２゜ＮＨ２ＣＨ２ＣＨｚＣＨ２ＣＨ２ＮＨｚ 、
ＮＬＣＬＣＬＣＬＣＩＩ２ＣＬＣＬＮＬ。0-CH30C6H4NH2, m-Cl, 0CJnNH
2, p-CHsOCsllJH2゜o CIC611
4NtJ2. m CIC5lLNR2, p CI
C611JJI2゜2,6-(Cl5)2C6H,N
H2,2,4,6-(CH3), C6112NH2, etc., and aliphatic and aromatic diamines, e.g. NH2
CH2CH2N1+2. NH, CH2CH2C112
N112゜NH2CH2CHzCH2CH2NHz,
NLCLCLCLCII2CLCLNL.
ｏ Ｎｌｌ２ＣＩｌＨ４ＮＨ２、ｒａ ＮＨｚＣｓ
）Ｉ＜Ｎ１１ｚ 、 ｐＮＩＩ２ＣｓＨ４Ｎｌ１２など
をあげることができるが、これらに限定されるものでは
ない。o Nll2CIlH4NH2, ra NHzCs
)I<N11z, pNII2CsH4Nl12, etc., but are not limited to these.
第二級アミンとしては、脂肪族鎖状および環状アミン、
例えば、（ＣＩ＋３）２ＮＨ、（Ｃ２１１５）２Ｎ１１
、 （Ｃ，Ｈ５）２ＮＩ＋。Secondary amines include aliphatic chain and cyclic amines,
For example, (CI+3)2NH, (C2115)2N11
, (C,H5)2NI+.
（ｎ Ｃ３Ｈ？＞２ＮＨ、（ｎ Ｃ＜ＨｓｈＮＨ、
（ｉｓｏ Ｃ４Ｈ９）２ＮＨ。(n C3H?>2NH, (n C<HshNH,
(iso C4H9)2NH.
（ｔ Ｃ＜Ｈｉ）２Ｎｆｌ 、 （ｎ Ｃ５Ｈｓ）
２Ｎｌｌ 、 （ｎ Ｃｓ１ｌ＋ １）２ＮＩ＋ 。(t C<Hi)2Nfl, (n C5Hs)
2Nll, (n Cs1l+ 1)2NI+.
（ｎ Ｃ，Ｈ＋ ５）ｚＮ）ｆ 、 （ｃｙｃｌｏ
ＣＪｈ ＋）（ＣＨｓ）ＮＨ。(n C, H+ 5)zN)f , (cyclo
CJh+)(CHs)NH.
（ＣＩ＋、）（Ｃ２Ｈ５）Ｎ１１ 、 （Ｃ２１１５）
（Ｃ，１Ｉ５）Ｎ１１など、芳香族アミン、例えば、（
Ｃ，Ｈ５）（ＣＨ３）ＮＦＩ 、 （Ｃ，Ｈ６ＣＨ２）
（ＣＨ３）ＮＨ。(CI+,)(C2H5)N11, (C2115)
Aromatic amines such as (C,1I5)N11, e.g.
C,H5)(CH3)NFI, (C,H6CH2)
(CH3)NH.
（ｏ−Ｃ１１３Ｃ，ｌｌ４）（Ｃ１１３）Ｎ１１ 、（
ｗ＋−ＣＩ！、Ｃ，１Ｉ４）（ＣＩ！、）Ｎｌｌ 。(o-C113C,ll4)(C113)N11 , (
w+-CI! ,C,1I4)(CI!,)Nll.
（ｐ−ＣＨｓＣ，Ｈ４）（ＣＨｓ）ＮＨ、（ｏ−Ｃ１，
ＯＣ，Ｌ）（Ｃ■、）ＮＨ。(p-CHsC,H4)(CHs)NH, (o-C1,
OC,L)(C■,)NH.
（Ｃ６１１，）２ＮＨなと、および複素環式アミン、例
えば、本発明に有用なパラジウムの化合物としては、Ｐ
ｄＣｌ２． ＰｄＢｒ２． ＰｄＩ２． Ｐｄ（ＯＣＯ
ＣＨ＊）２゜Ｐｄ（ＣＨ２ＣＯＣ）Ｉ２ＣＯＣＲ，）２
に２ＰｄＣ１，、Ｋ２ＰｄＣ１，、Ｋ２Ｐｄ（Ｎｏ３）
４などの無機塩、Ｐｃ１ＣＩ２（Ｃ２１１，）２ 、
Ｐｄ（π−Ｃ，ＩＩ、）２゜ＰｄＣｌ２（Ｃ−Ｈ１２）
、 Ｐｄ（ＣｓＨ４２）ｚなどの有機配位子錯体、Ｐ
ｄＣｌ２（ＮＨ３）２． ＰｄＣ１ｚ［Ｎ（Ｃ２１１５
）、］２．Ｐｄ（ＮＯｚ）ｚ（ＮＨ１３）ｓなどのＮ−
配位錯体、Ｐｄ［Ｐ（ＣＨ３）３コ、。(C611,)2NH, and heterocyclic amines, such as palladium compounds useful in the present invention, include P
dCl2. PdBr2. PdI2. Pd(OCO
CH*)2゜Pd(CH2COC)I2COCR,)2
2PdC1,,K2PdC1,,K2Pd(No3)
Inorganic salts such as 4, Pc1CI2(C211,)2,
Pd(π-C, II,)2゜PdCl2(C-H12)
, organic ligand complexes such as Pd(CsH42)z, P
dCl2(NH3)2. PdC1z[N(C2115
), ]2. N- such as Pd(NOz)z(NH13)s
Coordination complex, Pd[P(CH3)3.
ｐｄ［Ｐ（Ｃ２■Ｓ）３］４． Ｐｄ［Ｐ（ｎ Ｃ３
Ｈ７）３］４ 。pd[P(C2■S)3]4. Pd[P(n C3
H7)3]4.
Ｐｄ［Ｐ（ｉｓｏ−ＣＪｔ）＋］４． Ｐｄ［Ｐ（ｎ
ＣＪｓ）ｚ］４゜Ｐｄ［Ｐ（Ｃｓｌｌｓ）、］４．
ＰｄＣＯ２［Ｐ（Ｃ−Ｈｓ）３］ｚ 。Pd[P(iso-CJt)+]4. Pd[P(n
CJs)z]4°Pd[P(Cslls), ]4.
PdCO2[P(C-Hs)3]z.
Ｐｄ（ＣＪ−）［Ｐ（ＣｓＨｓ）、］２ 、ＰｄＣｌ２
［Ｐ（ＣＪｓ）３コ、。Pd(CJ-)[P(CsHs),]2, PdCl2
[3 P(CJs).
ＰｄＣｌ２［Ｐ（ｎ Ｃ４Ｈ’９）３］２ 、 Ｐｄ
Ｂｒｚ［Ｐ（Ｃ，）Ｉｓ）ｚ］ｚ １ＰｄＢｒ２［Ｐ（
ｎ−Ｃ４Ｈ６）、コ２ 、ＰｄＣｌ２［Ｐ（ＯＣＲ−
）、コ、。PdCl2[P(n C4H'9)3]2, Pd
Brz[P(C,)Is)z]z 1PdBr2[P(
n-C4H6), Co2, PdCl2[P(OCR-
),Ko,.
Ｐｄ１２［Ｐ（ＯＣＨ３）ｆｆ］２ 、 ＰｄＣ１（Ｃ
６Ｈ５）［Ｐ（Ｃ６ＪＩ５）３］２ノ如き三価のホスフ
ィン化合物を配位子とする錯体などを挙げることができ
るが、これらに限定されるものではない。Pd12[P(OCH3)ff]2, PdC1(C
Examples include, but are not limited to, complexes having a trivalent phosphine compound such as 6H5)[P(C6JI5)3]2 as a ligand.
多座配位リン化合物としては、−最大、（式中、Ｒ４，
Ｒｓ 、 Ｒ？およびＲ６は炭素数１〜２゜の脂肪族炭
化水素基、芳香族炭化水素基、または脂環族炭化水素基
であり、Ｒ６は二価の炭化水素基である）で表される２
座配位の燐化合物も有効である。このような化合物の具
体例としては、（ＣＨ，）２ＰＣＨ２Ｐ（ＣＨ３）２
、 （Ｃ２ＨｓｈＰ（ＣＨｚ）２Ｐ（Ｃ２ｕ、＞２゜（
Ｃｓｔｌｓ）２Ｐ（ＣＨ２）ｚＰ（Ｃｓｌｌｓ）２．
（ｎ Ｃ４Ｈｓ）ｚＰ（ＣＨｚ）２Ｐ（ｎ Ｃ４Ｈ
１１）’２ 、 （ｔ ＣｔＨり２Ｐ（ＣＨ２）２Ｐ
（ｔ Ｃ４Ｈ９）２ 。As a polydentate phosphorus compound, -max, (in the formula, R4,
Rs, R? and R6 is an aliphatic hydrocarbon group, aromatic hydrocarbon group, or alicyclic hydrocarbon group having 1 to 2 carbon atoms, and R6 is a divalent hydrocarbon group).
Coordinated phosphorus compounds are also effective. Specific examples of such compounds include (CH,)2PCH2P(CH3)2
, (C2HshP(CHz)2P(C2u, >2°(
Cstls)2P(CH2)zP(Cslls)2.
(n C4Hs)zP(CHz)2P(n C4H
11)'2, (t CtHri2P(CH2)2P
(tC4H9)2.
（ＣｓＨｓ）２Ｐ（ＣＨ２）ｓＰ（ＣＪｓ）２． （ｎ
Ｃ４Ｈ９）２Ｐ（ＣＨ２）３Ｐ（ｎ ＣＪｓ）ｚ
、 （ＣｓＨｓ）２Ｐ（Ｃｆｈ）４Ｐ（ＣＪｓ）ｚ
。(CsHs)2P(CH2)sP(CJs)2. (n
C4H9)2P(CH2)3P(n CJs)z
, (CsHs)2P(Cfh)4P(CJs)z
.
（Ｃ２Ｈ５）２Ｐ （Ｃｔｌ□）４Ｐ（Ｃ２１１５）２
、 （Ｃ６Ｈ５）２Ｐ（Ｃ１１□）５Ｐ（Ｃ，ｌｌ、
）２゜（ｎ Ｃ＜Ｈｓ）２Ｐ（ＣＨｚ）ｓＰ（ｎ
Ｃ４Ｈ９）２ 、 （Ｃ２Ｈ５）２Ｐ（Ｃ１２）ＳＰ（
Ｃ２１１，）２などを挙げることができるが、これらに
限定されるものではない。(C2H5)2P (Ctl□)4P(C2115)2
, (C6H5)2P(C11□)5P(C,ll,
)2゜(n C<Hs)2P(CHz)sP(n
C4H9)2, (C2H5)2P(C12)SP(
Examples include, but are not limited to, C211, )2, etc.
本発明の方法に含まれる反応は、アルカリを添加するこ
とにより、有利に進行する。この目的に用いることので
きるアルカリとしては以下のようなものを挙げることが
できる。即ち、水酸化アンモニウム塩、例えば、（ＣＩ
、）、ＮＯＨ、（Ｃ２Ｈ５）４ＮＯ１ｌ 。The reactions involved in the process of the invention proceed advantageously by adding an alkali. Examples of alkalis that can be used for this purpose include the following. That is, ammonium hydroxide salts, such as (CI
), NOH, (C2H5)4NO1l.
（Ｃ，Ｈ５）４ＮＯＲ、（ｎ−Ｃ，ｌ（、）、ＮＯＨ、
（ｉｓｏ−Ｃ３Ｈ，）４ＮＯＨ。(C,H5)4NOR, (n-C,l(,),NOH,
(iso-C3H,)4NOH.
（ｎ−Ｃ４１１１）４ＮＯＲ、（ｉｓｏ−Ｃ４Ｈ９）４
ＮＯＨ、（ｔ−Ｃ４１１！１）４ＮＯＩ＋。(n-C4111)4NOR, (iso-C4H9)4
NOH, (t-C411!1)4NOI+.
（ＣＨ３）（ｎ Ｃ４ｔｌｓ）３ＮＯＨ、（ＣＪｓ）
２（ｎ Ｃ３Ｈ２）２Ｎｏｎ 。(CH3) (n C4tls)3NOH, (CJs)
2(n C3H2)2Non.
（Ｃ，Ｈ，ＣＨ２）（ＣＬ）、ＮＯＨなど、アルカリ金
属化合物、例えば、Ｎａ０１１ 、 ＫＯＨ、ＬｉＯＨ
、ＮａＨ、Ｋｌ 、 ＬｉＨ、Ｎａｌ１１１． 。Alkali metal compounds such as (C,H,CH2)(CL), NOH, e.g. Na011, KOH, LiOH
, NaH, Kl, LiH, Nal111. .
Ｌｉ＾Ｉ８．など、有機アルカリ金属化合物、例えば、
Ｃ１ｌ、Ｌｉ 、 ＣＪ５Ｌｉ 、 ｎ−ＣＪｙＬｉ
、 ｎ−Ｃ４ＬＬｉなど、アルカリ金属アルコキシド、
例えば、ＣＨ＊ＯＮａ 。Li^I8. Organic alkali metal compounds such as, for example,
C1l, Li, CJ5Li, n-CJyLi
, an alkali metal alkoxide such as n-C4LLi,
For example, CH*ONa.
Ｃ２１１ｓＯＮａ 、 ｎ Ｃ４Ｈ９０Ｎａ 、 Ｃ
Ｊ、ＯＬ！ 、 Ｃ２１１５ＯＫなど、フェノール類の
アルカリ金属塩、例えばＣＪｓＯＮａ 。C211sONa, n C4H90Na, C
J.OL! , C2115OK, alkali metal salts of phenols, such as CJsONa.
Ｃｓ１ｌｓＯＫ 、 Ｃａ１１５０Ｌｉ 、 ｏ−ＣＩ
、ＣｓＨ４０Ｎａ 、 ｎ−Ｃ１１−Ｃ６１１４ＯＮａ
。Cs1lsOK, Ca1150Li, o-CI
, CsH40Na, n-C11-C6114ONa
.
ｐ ＣＨ：＋Ｃ６Ｈ４０Ｎａ 、 ｏ ＣＨｙＣ６
Ｈ４０Ｋ 、 ｍ ＣＨｉＣｓＨ４ＯＫ 。p CH:+C6H40Na, o CHyC6
H40K, mCHiCsH4OK.
ｐ−Ｃ１１３ＣｓＨ＜ＯＫなどを挙げることができるが
、もちろんこれらに限られるものではない。Examples include, but are not limited to, p-C113CsH<OK.
アルカリ添加量は、パラジウム化合物のパラジウム金属
に対するモル比で１〜５００、・好ましくは１〜２００
の量であるのが望しい。The amount of alkali added is 1 to 500, preferably 1 to 200, in molar ratio of palladium compound to palladium metal.
It is desirable that the amount of
本発明の方法においては、上記の如きパラジウム化合物
と多座配位リン化合物を組み合わせてなる触媒を、アリ
ル型アルコールの１モルに対して１ ／１０〜１ ／１
００，０００、好ましくは１１５ｏ〜１／２０．０００
モルの量で用いるのが望ましい。また、この場合、多座
配位リン化合物は、パラジウム化合物のパラジウム金属
に対するモル比で、１〜１００、好ましくは１〜２０の
量で用いるのが望ましく、パラジウム化合物中に多座配
位リン化合物が含まれている場合は更に多座配位リン化
合物を用いる必要がないこともある。本発明においては
、多座配位リン化合物を用いることが必須であるが、単
座配位リン化合物が共存しても何らさしつがえない。In the method of the present invention, the catalyst consisting of a combination of a palladium compound and a polydentate phosphorus compound as described above is used in an amount of 1/10 to 1/1 per mole of allyl alcohol.
00,000, preferably 115o to 1/20.000
Preferably, it is used in molar amounts. Further, in this case, the polydentate phosphorus compound is desirably used in an amount of 1 to 100, preferably 1 to 20 in molar ratio of the palladium compound to palladium metal. is included, it may not be necessary to further use a polydentate phosphorus compound. In the present invention, it is essential to use a polydentate phosphorus compound, but there is no problem even if a monodentate phosphorus compound coexists.
本発明の方法において、アミンは、アリル型アルコール
に対するモル比で１／１００〜１００、好ましくは１／
１０〜１０の量で用いられるのが望ましい。In the method of the present invention, the amine is used in a molar ratio of 1/100 to 100, preferably 1/1 to the allylic alcohol.
Preferably, it is used in an amount of 10 to 10.
アリル型アルコールとアミンとの反応は、０〜２００℃
、好ましくは３０〜１５０℃の温度で行われるのがよい
。The reaction between allylic alcohol and amine is carried out at 0 to 200°C.
, preferably at a temperature of 30 to 150°C.
本発明の方法は、溶媒の存在下にもしくは溶媒の存在な
しに実施することができる。有用な溶媒の例としては、
メタノール、エタノール、ｎ−プロピルアルコール、１
ｓｏ−プロピルアルコール、ｎ−ブチルアルコール、１
ｓｏ−ブチルアルコール、Ｌ−ブチルアルコール、エチ
レングリコール、プロピレングリコール等のアルコール
類、ベンゼン、トルエン、ヘキサン等の芳香族もしくは
脂肪族炭素水素類、アセトニトリル、ベンゾニトリル、
アクリロニトリル、アジポニトリル等のニトリル類。The method of the invention can be carried out in the presence of a solvent or without the presence of a solvent. Examples of useful solvents include:
methanol, ethanol, n-propyl alcohol, 1
so-propyl alcohol, n-butyl alcohol, 1
Alcohols such as so-butyl alcohol, L-butyl alcohol, ethylene glycol, propylene glycol, aromatic or aliphatic hydrocarbons such as benzene, toluene, hexane, acetonitrile, benzonitrile,
Nitriles such as acrylonitrile and adiponitrile.
クロロベンゼン、ジクロロベンゼン、四塩化炭素、クロ
ロホルム、ジクロロメタン等のハロゲン化炭化水素類、
ジブチルエーテル、ジオキサン、ジエチレングリコール
ジメチルエーテル、トリエチレングリコールジメチルエ
ーテル等のエーテル類、トリエチルアミン、トリプロピ
ルアミン、トリブチルアミン、Ｎ、Ｎ−ジメチルアニリ
ン等の三級アミン類および水を挙げることができるが、
これらに限定されるものではない。Halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, carbon tetrachloride, chloroform, dichloromethane,
Examples include ethers such as dibutyl ether, dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tertiary amines such as triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, and water.
It is not limited to these.
本発明の方法によれば、アリル型アルコールとアミンと
を原料として用いて、塩の副生を伴うことなく、アリル
型アミンを収率よく得ることができ、極めて効率的がっ
安価にアリル型アミンを製造することができる。According to the method of the present invention, allyl-type amines can be obtained in high yields without salt by-products using allyl-type alcohols and amines as raw materials, and allyl-type amines can be obtained in high yields extremely efficiently and inexpensively. Amines can be produced.
以下、実施例を挙げて、本発明をさらに説明する。もち
ろん、本発明はこれらの例によって限定されるべきもの
ではない。The present invention will be further explained below with reference to Examples. Of course, the invention should not be limited to these examples.
実施例１〜１３
３．０ｇ（５２，５ミリモル）のモノアリルアミンおよ
び８．４ｇ（１４４，６ミリモル）のアリルアルコール
を、５ｇのプロピレングリコールおよび３．６ｇの水か
らなる溶媒中において、下記の第１表に示す触媒および
アルカリの存在下に、１１０℃で２時間反応させた。得
られた生成物の組成およびアリルアルコールの転化率を
第２表に示す。Examples 1-13 3.0 g (52.5 mmol) of monoallylamine and 8.4 g (144.6 mmol) of allyl alcohol were prepared as follows in a solvent consisting of 5 g of propylene glycol and 3.6 g of water. The reaction was carried out at 110° C. for 2 hours in the presence of the catalyst and alkali shown in Table 1. The composition of the product obtained and the conversion rate of allyl alcohol are shown in Table 2.
以下余日
尚、表中、ＤＰＰＢは１，４−ビス（ジフェニルホスフ
ィノ）ブタン、叶ＰＥは１．２−ビス（ジフェニルホス
フィノ）エタン、ＴＢＡＨＯはテトラブチルアンモニウ
ムハイドロオキサイドである。Hereinafter, in the table, DPPB is 1,4-bis(diphenylphosphino)butane, PE is 1,2-bis(diphenylphosphino)ethane, and TBAHO is tetrabutylammonium hydroxide.
第２表
実施例１４および１５
３．７９ｇ （５１，８ミリモル）のジエチルアミンお
よび８．４ｇ（１４４，６ミリモル）のアリルアルコー
ルを、５ｇのプロピレングリコールおよび３．６ｇの水
からなる溶媒中において、下記の第３表に示す触媒およ
びアルカリの存在下に、１１０℃で１時間反応させた。Table 2 Examples 14 and 15 3.79 g (51.8 mmol) diethylamine and 8.4 g (144.6 mmol) allyl alcohol in a solvent consisting of 5 g propylene glycol and 3.6 g water. The reaction was carried out at 110° C. for 1 hour in the presence of the catalyst and alkali shown in Table 3 below.
得られた生成物の組成およびアリルアルコールの転化率
を第４表に示す。Table 4 shows the composition of the product obtained and the conversion rate of allyl alcohol.
第３表
表中、υ）’ＰＩＪは１．４−ビス（ジフェニルホスフ
ィカプタンである。In Table 3, υ)'PIJ is 1,4-bis(diphenylphosphcaptan).
第４表
実施例１６
下記、
Ｐｄ（ＣＨ２ＣＯＣＨ２ＣＯＣＨ，）２３．１ｍｇ（０
，０１ミリモル）ＴＢＡＨｏ １３
０ｍｇ（０，５０ミリモル）プロピレングリコール
５ｍＺ
水 ３．６ｍＮアリルアル
コール ８．４１ｇ（１４４，８ミリモル）Ｎ−
メチルアニリン ５．５７ｇ（５２，０ミリモル）
からなる系を１１０℃で２時間の反応に付した。Table 4 Example 16 Below, Pd (CH2COCH2COCH,) 23.1 mg (0
,01 mmol) TBAHo 13
0 mg (0,50 mmol) propylene glycol
5mZ Water 3.6mN Allyl alcohol 8.41g (144.8 mmol) N-
Methylaniline 5.57g (52.0 mmol)
The system consisting of was subjected to a reaction at 110°C for 2 hours.
アリルアルコールの転化率は３６．４％であり、生成物
は２．６９ｇ （２５，１ミリモル）のＮ−メチル−Ｎ
−アリルアニリンと１．３５ｇ （１３，８ミリモル）
のジアリルエーテルを含んでいた。The conversion of allyl alcohol was 36.4% and the product was 2.69 g (25.1 mmol) of N-methyl-N
- allylaniline and 1.35 g (13,8 mmol)
It contained diallyl ether.
実施例１７
下記、
Ｐｃｔ（ＣＩ＋２ＣＯＣ１１２ＣＯＣＨ３）２１５．３
ｍｇ（０，０５ミリモル）ＴＢ＾１１０
１３０ｍｇ（０，５０ミリモル）１．４−ブタンジ
オール１０社
アリルアルコール ８．４０ｇ（１４４，８ミリ
モル）ジエチルアミン ３．７９ｇ（５１，８
ミリモル）からなる系を１１０℃で２時間の反応に付し
た６アリルアルコールの転化率は３４．８％であり、生
成物は５．２ｇ（４６，０ミリモル）のアリルジエチル
アミンと０．１ｇ （１，０ミリモル）のジアリルエー
テルを含んでいた。Example 17 Below, Pct(CI+2COC112COCH3)215.3
mg (0.05 mmol) TB^110
130 mg (0,50 mmol) 1,4-butanediol 10 companies Allyl alcohol 8.40 g (144,8 mmol) Diethylamine 3.79 g (51,8
The conversion rate of hexaallylic alcohol was 34.8% when the system consisting of 5.2 g (46.0 mmol) of allyl diethylamine and 0.1 g ( 1.0 mmol) of diallyl ether.
実施例１８
下記、
ＰｄＣｌ２３．５ｍｇ（０，０２ミリモル）１４−ビス
（ジフェニ
ルポスフィノ）ブタン ２５．６…ｇ（０，０６ミリ
モル）ＴＭΔｔｌｏ ４５．５ｍ
ｇ（０，５０ミリモル）１．３−ブタンジオール ５ｍ
ｌ
メタリルアルコール １０．８ｇ（１５０，０ミリモ
ル）ジエチルアミン ３．８０ｇ（５２゜１ミ
リモル）からなる系を１００℃で４時間の反応に付した
。Example 18 Below, PdCl 23.5 mg (0.02 mmol) 14-bis(diphenylphosphino)butane 25.6...g (0.06 mmol) TMΔtlo 45.5 m
g (0.50 mmol) 1,3-butanediol 5m
A system consisting of 10.8 g (150.0 mmol) of methallyl alcohol and 3.80 g (52.0 mmol) of diethylamine was subjected to a reaction at 100° C. for 4 hours.
メタリルアルコールの転化率は３２．３％であり、生成
物は５．９ｇ（４６，５ミリモル）のメタリルジエチル
アミンと０．１ｇ （１，０ミリモル）のジアリルエー
テルを含んでいた。The conversion of methallyl alcohol was 32.3% and the product contained 5.9 g (46.5 mmol) methallyl diethylamine and 0.1 g (1.0 mmol) diallyl ether.
Claims (1)
立に、水素原子、炭素数１〜８の脂肪族炭化水素基、脂
環族炭化水素基、または芳香族炭化水素基を表す〕で示
されるアリル型アルコールと第一級アミンおよび／また
は第二級アミンとを、パラジウムの化合物と多座配位リ
ン化合物の存在下に、反応させることを特徴とするアリ
ル型アミンの製造法。[Claims] 1. The following formula, ▲ Numerical formula, chemical formula, table, etc.▼ [In the above formula, R_1, R_2 and R_3 each independently represent a hydrogen atom or an aliphatic hydrocarbon having 1 to 8 carbon atoms. group, alicyclic hydrocarbon group, or aromatic hydrocarbon group] and a primary amine and/or a secondary amine, a palladium compound and a polydentate phosphorus compound. 1. A method for producing an allyl amine, which comprises reacting in the presence of an allyl amine.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62323833A JPH0757743B2 (en) | 1987-12-23 | 1987-12-23 | Method for producing allylic amine |
| DE88311646T DE3883724T2 (en) | 1987-12-11 | 1988-12-08 | Process for the preparation of allyl type amines. |
| EP88311646A EP0320269B1 (en) | 1987-12-11 | 1988-12-08 | Process for preparation of allyl type amine |
| US07/282,095 US4942261A (en) | 1987-12-11 | 1988-12-09 | Process for preparation of allyl type amine |
| KR1019880016446A KR890009827A (en) | 1987-12-11 | 1988-12-10 | Method for preparing allyl amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62323833A JPH0757743B2 (en) | 1987-12-23 | 1987-12-23 | Method for producing allylic amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01165555A true JPH01165555A (en) | 1989-06-29 |
| JPH0757743B2 JPH0757743B2 (en) | 1995-06-21 |
Family
ID=18159105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62323833A Expired - Fee Related JPH0757743B2 (en) | 1987-12-11 | 1987-12-23 | Method for producing allylic amine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0757743B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010510280A (en) * | 2006-11-23 | 2010-04-02 | チバ ホールディング インコーポレーテッド | Method for producing N-allyl sterically hindered tertiary amine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037641A (en) * | 1973-06-25 | 1975-04-08 |
-
1987
- 1987-12-23 JP JP62323833A patent/JPH0757743B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037641A (en) * | 1973-06-25 | 1975-04-08 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010510280A (en) * | 2006-11-23 | 2010-04-02 | チバ ホールディング インコーポレーテッド | Method for producing N-allyl sterically hindered tertiary amine |
| KR101454703B1 (en) * | 2006-11-23 | 2014-10-27 | 시바 홀딩 인코포레이티드 | Process for the preparation of tertiary N-allyl sterically hindered amines |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0757743B2 (en) | 1995-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8586742B2 (en) | Process for preparing amines from alcohols and ammonia | |
| KR101821987B1 (en) | Metal catalysts for selective formation of cyclic carbonates, process for preparing cyclic carbonate using the same and use of cyclic carbonate | |
| EP0581131B1 (en) | A process for producing alkylene carbonates | |
| Sroor et al. | Lanthanide (III)-bis (cyclopropylethinylamidinates): Synthesis, structure, and catalytic activity | |
| KR101839877B1 (en) | New organocatalysts and method of manufacturing alkylene carbonates using the same | |
| JPH04211075A (en) | Preparation of alkylene carbonate | |
| JPH0161097B2 (en) | ||
| US4942261A (en) | Process for preparation of allyl type amine | |
| WO2003006420A1 (en) | Catalytic method to convert aryl compounds to aryl amines | |
| US6225499B1 (en) | Process for preparing aminoarylacetylenes | |
| Karmakar et al. | Aluminium alkyl complexes supported by imino-phosphanamide ligand as precursors for catalytic guanylation reactions of carbodiimides | |
| GB2082181A (en) | A process for the production of acetaldehyde and ethanol | |
| JPH01165555A (en) | Production of allyl type amine | |
| CA1208657A (en) | Process for the preparation of formamides | |
| US4355168A (en) | Process for preparing aryl- or heteroarylhexadienoic acids | |
| US4709087A (en) | Process for the synthesis of isocyanates and of isocyanate derivatives | |
| JPH01153660A (en) | Production of allyl-type amine | |
| US20190039990A1 (en) | Homogeneous iron catalysts for the conversion of methanol to methyl formate and hydrogen | |
| JPS632958A (en) | Production of allyl type amine | |
| US10266467B2 (en) | Synthesis of glycols via transfer hydrogenation of alpha-functional esters with alcohols | |
| KR101654787B1 (en) | Catalyst Composition Comprising Palladium Ketoiminate Complex and Preparation Method for Cross-Coupling Compound Using the Composition | |
| JPS58213745A (en) | Preparation of alpha-ketoamide | |
| JPS5982947A (en) | Catalyst and method for producing acetic acid by catalytic rearrangement of methyl formate | |
| US20190039991A1 (en) | Homogeneous iron catalysts for the conversion of ethanol to ethyl acetate and hydrogen | |
| JPS63307847A (en) | Production of p-aminostyrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |