JPH02222728A - Catalyst for positionally selective hydrogenation of carbon-carbon double bond - Google Patents
Catalyst for positionally selective hydrogenation of carbon-carbon double bondInfo
- Publication number
- JPH02222728A JPH02222728A JP4020789A JP4020789A JPH02222728A JP H02222728 A JPH02222728 A JP H02222728A JP 4020789 A JP4020789 A JP 4020789A JP 4020789 A JP4020789 A JP 4020789A JP H02222728 A JPH02222728 A JP H02222728A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carbon
- hexenol
- double bond
- trans
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 11
- 239000002798 polar solvent Substances 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- ZCHHRLHTBGRGOT-SNAWJCMRSA-N (E)-hex-2-en-1-ol Chemical compound CCC\C=C\CO ZCHHRLHTBGRGOT-SNAWJCMRSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 14
- VTIODUHBZHNXFP-NSCUHMNNSA-N 4-Hexen-1-ol, (E)- Chemical compound C\C=C\CCCO VTIODUHBZHNXFP-NSCUHMNNSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- VTIODUHBZHNXFP-UHFFFAOYSA-N trans-hex-4-en-1-ol Natural products CC=CCCCO VTIODUHBZHNXFP-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- -1 poly(N-vinyl-2-pyrrolidone) Polymers 0.000 description 7
- JHEPBQHNVNUAFL-AATRIKPKSA-N (e)-hex-1-en-1-ol Chemical compound CCCC\C=C\O JHEPBQHNVNUAFL-AATRIKPKSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 5
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 5
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000005792 Geraniol Substances 0.000 description 2
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229940113087 geraniol Drugs 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- BNWJOHGLIBDBOB-UHFFFAOYSA-N myristicin Chemical compound COC1=CC(CC=C)=CC2=C1OCO2 BNWJOHGLIBDBOB-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-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
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 235000000484 citronellol Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、炭素−炭素二重結合を有し、かつ親水性官能
基を有する化合物を選択的に水素添加する触媒に関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a catalyst for selectively hydrogenating a compound having a carbon-carbon double bond and a hydrophilic functional group.
従来、不均一触媒系における炭素−炭素二重結合を有し
、かつ親水性官能基を有する脂肪族化合物の二重結合の
位置選択的水素添加は二重結合の周辺の立体的障害の差
により行われてきた。従って、立体的環境がほとんど等
価な二重結合を識別して水素添加することは非常に困難
であった。最近になって、コロイド状の金属触媒を水溶
性のポリマー［ポリ （Ｎ−ビニル−２−ピロリドン）
等］で修飾してミセル類似機能を有する触媒を調製し、
水溶液中において疎水部側の二重結合の位置選択的水素
添加を試みている例がある（ケミストリーレターズ（Ｃ
ｈｅａ＋１ｓｔｒｙ Ｌｅｔｔｅｒｓ）、１９８８年、
５７３ペ一ジ等１゜しかし、この触媒は適用できる物質
が長鎖の不飽和カルボン酸等であり、かつ二重結合の位
置がかなり離れたく例えばウンデセン酸の場合は２位と
１０位）化合物に限るため適用範囲が狭く、また、反応
後触媒を反応系から分離するのが困難であるという欠点
がある。Conventionally, regioselective hydrogenation of the double bond of aliphatic compounds having a carbon-carbon double bond and a hydrophilic functional group in a heterogeneous catalyst system has been carried out due to the difference in steric hindrance around the double bond. It has been done. Therefore, it has been very difficult to identify and hydrogenate double bonds whose steric environments are almost equivalent. Recently, colloidal metal catalysts have been synthesized into water-soluble polymers [poly(N-vinyl-2-pyrrolidone)].
etc.] to prepare a catalyst with micelle-like functions,
There is an example of attempting regioselective hydrogenation of a double bond on the hydrophobic side in an aqueous solution (Chemistry Letters (C
hea+1stry Letters), 1988,
Page 573, etc. 1゜However, this catalyst can only be applied to long-chain unsaturated carboxylic acids, and the double bonds are located quite far apart (for example, in the case of undecenoic acid, the 2nd and 10th positions). However, the range of application is narrow and it is difficult to separate the catalyst from the reaction system after the reaction.
［発明が解決しようとする問題点］
不均一反応系において、炭素−炭素二重結合を有する親
水性脂肪族化合物の親水部側の二重結合を選択的に水素
添加する触媒はこれまでまったく知られていない。しか
し、この触媒が得られると、例えば香料として利用され
ているシトロネロールをゲラニオールより容易に得るこ
とができ、有機合成上で有用なものとなる。[Problems to be solved by the invention] Until now, no catalyst has been known that selectively hydrogenates the double bond on the hydrophilic side of a hydrophilic aliphatic compound having a carbon-carbon double bond in a heterogeneous reaction system. It has not been done. However, once this catalyst is obtained, for example, citronellol, which is used as a fragrance, can be obtained more easily than geraniol, making it useful in organic synthesis.
本発明者らは、親水性官能基と炭素−炭素二重結合を有
する脂肪族化合物の親水部側の二重結合を選択的に水素
添加し、かつ、取扱いが容易な触媒を得ることを目的と
して鋭意研究した結果、本発明を完成するに室った〇
［問題を解決する手段］
すなわち、白金担持アルミナにカルボン酸を吸着させた
ことを特徴とし、親水性官能基と炭素−炭素二重結合と
を有する脂肪族化合物の親水性官能基の近傍にある炭素
−炭素二重結合を選択的に水素添加する触媒である（以
下、本触媒という）。The present inventors aimed to selectively hydrogenate the double bond on the hydrophilic side of an aliphatic compound having a hydrophilic functional group and a carbon-carbon double bond, and to obtain a catalyst that is easy to handle. As a result of intensive research, we have completed the present invention. [Means for solving the problem] In other words, it is characterized by adsorbing carboxylic acid to platinum-supported alumina, and it is characterized by a hydrophilic functional group and a carbon-carbon double bond. This catalyst selectively hydrogenates carbon-carbon double bonds near the hydrophilic functional group of an aliphatic compound having a bond (hereinafter referred to as the present catalyst).
本触媒のｒＡ製は、白金担持アルミナとカルボン酸を非
プロトン性極性溶媒中に混ぜてかくはんした後、濾過、
洗浄して乾燥すればよい。反応はへ牛サン等の極性の低
い溶媒中で行う。反応生成物との分離は濾過する操作を
行うだけでよい。白金担持アルミナの白金担持量は重量
比０．１−１０％であればよく、望ましくはｌ−７％で
ある。カルボン酸は特に限定されるものではない。炭素
数３−２０の脂肪酸または芳香族カルボン酸であればよ
いが、６−１４の脂肪酸または芳香族カルボン酸が好ま
しい。非プロトン性極性溶媒としては、ジメチルホルム
アミド、ジメチルスルホキシドが挙げられる。This catalyst made by rA mixes platinum-supported alumina and carboxylic acid in an aprotic polar solvent, stirs the mixture, and then filtrate.
Just wash and dry. The reaction is carried out in a less polar solvent such as hexane. Separation from the reaction product can be achieved by simply performing a filtration operation. The amount of platinum supported on the platinum-supported alumina may be 0.1-10% by weight, preferably 1-7% by weight. Carboxylic acids are not particularly limited. Any fatty acid or aromatic carboxylic acid having 3 to 20 carbon atoms may be used, but fatty acids or aromatic carboxylic acids having 6 to 14 carbon atoms are preferred. Examples of the aprotic polar solvent include dimethylformamide and dimethyl sulfoxide.
本触媒は、アルミナの表面にカルボン酸が静電的に吸着
しているものと考えられる。従って、本触媒は、極性溶
媒中ではカルボン酸が脱離するかへキサン等の極性の低
い溶媒中においてカルボン酸の脱離はほとんどなく、反
応中の触゛媒の安定性には問題はない。本触媒の反応は
カルボン酸修飾により構築される反応場の効果によって
、比較的近接していて、なおかつ立体的環境の類似して
いる二重結合のうち親水性官能基側を位置選択的に接触
水素添加を行うことができる特徴を有する。In this catalyst, carboxylic acid is considered to be electrostatically adsorbed on the surface of alumina. Therefore, with this catalyst, carboxylic acid is eliminated in a polar solvent, but there is almost no elimination of carboxylic acid in a less polar solvent such as hexane, and there is no problem with the stability of the catalyst during the reaction. . The reaction of this catalyst uses the effect of the reaction field constructed by carboxylic acid modification to regioselectively contact the hydrophilic functional group side of double bonds that are relatively close and have similar steric environments. It has the characteristic of being able to perform hydrogenation.
反応の対象である炭素−炭素二重結合を有し、かつ親水
性官能基を有する化合物は特に限定されるものではない
、親水性官能基としては水酸基、カルボキシル基、アミ
７基が挙げられ、好ましくは水酸基である。The compound having a carbon-carbon double bond that is the target of the reaction and having a hydrophilic functional group is not particularly limited. Examples of the hydrophilic functional group include a hydroxyl group, a carboxyl group, and an amide group, Preferably it is a hydroxyl group.
以下実施例により説明する。This will be explained below using examples.
［実施例１コ
１免二鼠１
５％の白金担持アルミナ（日本エンゲルノ＼ルド社製）
１．０ｇをデカン酸１００ｍｇのジメチルホルムアミ
ド溶液１０＋ｎｌに加えて１晩ゆっくりかくはんした。[Example 1 1 5% platinum-supported alumina (manufactured by Nippon Engelno/Rudo Co., Ltd.)
1.0 g was added to 10+nl of a solution of 100 mg of decanoic acid in dimethylformamide and stirred slowly overnight.
その後、不溶固体を濾別しジメチルホルムアミド１０ｍ
１で洗浄した。濾別した固体は十分乾燥させ、デカン酸
修飾白金担持アルミナ触媒１．０４ｇを得た。デカン酸
に代え、ヘキサン酸、ミリスチン酸、安息香酸、アジピ
ン酸により同様にカルボン酸修飾白金担持アルミナ触媒
を調製した。After that, insoluble solids were separated by filtration and dimethylformamide (10ml) was added.
Washed with 1. The filtered solid was sufficiently dried to obtain 1.04 g of a decanoic acid-modified platinum-supported alumina catalyst. Carboxylic acid-modified platinum-supported alumina catalysts were similarly prepared using hexanoic acid, myristic acid, benzoic acid, and adipic acid instead of decanoic acid.
［実施例２］
触媒１０ ｍ ｇ、各挿ヘキセノール０．２ｇ及びトリ
デカン０．１ｇをヘキサン２０ｍ＋１中で混ぜ、大過剰
の水素雰囲気下零度でかくはんし、反応の経時変化をガ
スクロマトグラフで分析する。デカン酸修飾触媒とコン
トロール触媒の結果は図１及び図２に示した。[Example 2] 10 mg of catalyst, 0.2 g of each intercalated hexenol, and 0.1 g of tridecane are mixed in 20 m+1 hexane, stirred at zero temperature in a large excess hydrogen atmosphere, and the time course of the reaction is analyzed by gas chromatography. The results of the decanoic acid modified catalyst and the control catalyst are shown in FIGS. 1 and 2.
本触媒には、コントロール触媒に比ベニ重結合の位置の
違いによる選択的水素添加の機能が有ることがわかる。It can be seen that this catalyst has a selective hydrogenation function due to the difference in the position of the double bond relative to the control catalyst.
［実施例３］
触媒１０ｍｇ、 ）ランス
２−ヘキセノール０１ｇ１
トランス
４−へ半々ノール０．１ｇ及びトリデカン０．１ｇをヘ
キサン２０ｍ１中で混ぜ、大過剰の水素雰囲気下零度で
かくはんし、反応の経時変化をガスクロマトグラフで分
析する。デカン酸修飾触媒とフントロール触媒の結果は
図３及び図４に示した。[Example 3] 10 mg of catalyst, 0.1 g of trans 2-hexenol, 0.1 g of half-trans 4-hexenol, and 0.1 g of tridecane were mixed in 20 ml of hexane, stirred at zero temperature under a large excess hydrogen atmosphere, and the time course of the reaction was measured. is analyzed using a gas chromatograph. The results of the decanoic acid modified catalyst and Funtrol catalyst are shown in FIGS. 3 and 4.
本触媒には、親水性官能基より近い位置にある炭素−炭
素二重結合を選択的に水素添加する機能が有ることがわ
かる。It can be seen that this catalyst has a function of selectively hydrogenating carbon-carbon double bonds located closer to the hydrophilic functional group.
［実施例４］ ミリスチン アルミナ によるト 触媒１ｈｇ、）ランス ２−へ牛セノールＯ，Ｉｇ。[Example 4] myristicin Made of alumina Catalyst 1hg,) Lance 2-to bovine senol O, Ig.
トランス ４−へキ七ノールＯ，Ｉｇ及びトリデカン０
、１ｇをヘキサンＺｈｌ中で混ぜ、大過剰の水素雰囲気
下零度でか（はんし、反応の経時変化をガスクロマトグ
ラフで分析する。ミリスチン酸修飾触媒の結果は図６に
示した。Trans 4-hequinanol O, Ig and tridecane 0
, 1 g was mixed in hexane (Zhl) at zero temperature in a large excess of hydrogen atmosphere.The time course of the reaction was analyzed by gas chromatography.The results for the myristic acid-modified catalyst are shown in Figure 6.
［実施例６］
触媒１０ｍｇ、 ）ランス ２−へ牛セノールｏ、１
ｇ。[Example 6] Catalyst 10 mg, ) lance 2- to bovine senol o, 1
g.
トランス ４−へキセノール０．１ｇ及びトリデカン０
、１ｇをヘキサン２０ｍ１中で混ぜ、大過剰の水素雰囲
気下零度でかくはんし、反応の経時変化をガスクロマト
グラフで分析する。ヘキサン酸修飾触媒の結果は図５に
示した。Trans 4-hexenol 0.1g and tridecane 0
, 1 g in 20 ml of hexane, stirred at zero temperature in a large excess hydrogen atmosphere, and the time course of the reaction was analyzed by gas chromatography. The results of the hexanoic acid modified catalyst are shown in FIG.
［実施例５コ
触媒１０Ｂ、 ）ランス ２−ヘキセノール０．１ｇ
。[Example 5 Cocatalyst 10B, ) Lance 2-hexenol 0.1 g
.
トランス ４−ヘキセノールＯ，Ｉｇ及びトリデカン０
．１ｇをヘキサン２０ａ＋１中で混ぜ、大過剰の水素雰
囲気下零度でかくはんし、反応の経時変化をガスクロマ
トグラフで分析する。アジピン酸修飾触媒の結果は図７
に示した。trans 4-hexenol O, Ig and tridecane 0
．． 1 g was mixed in 20a+1 hexane, stirred at zero temperature in a large excess of hydrogen atmosphere, and the time course of the reaction was analyzed by gas chromatography. The results of the adipic acid modified catalyst are shown in Figure 7.
It was shown to.
［実施例７］
触媒１０ｎ＋ｇ、 ）ランス ２−ヘキセノール０．
１ｇ。[Example 7] Catalyst 10n+g, ) Lance 2-hexenol 0.
1g.
トランス ４−ヘキセノール０．１ｇ及びトリデカン０
、１ｇをヘキサン２０ｍ１中で混ぜ、大過剰の水素雰囲
気下零度でかくはんし、反応の経時変化をガスクロマト
グラフで分析する。安息香酸修飾触媒の結果は図８に示
した。Trans 4-hexenol 0.1g and tridecane 0
, 1 g in 20 ml of hexane, stirred at zero temperature in a large excess hydrogen atmosphere, and the time course of the reaction was analyzed by gas chromatography. The results of the benzoic acid modified catalyst are shown in FIG.
［実施例８］
触媒１０ ｒｓ ｇｓ ゲラニオール０．１ｇ及びトリ
デカン０．１ｇをヘキサン２０ｍ１中で混ぜ、大過剰の
水素雰囲気下零度でかくはんし、反応の経時変化をガス
クロマトグラフで分析する。デカン酸修飾触媒における
結果は図９に示した。[Example 8] Catalyst 10 rs gs 0.1 g of geraniol and 0.1 g of tridecane are mixed in 20 ml of hexane, stirred at zero temperature in a large excess hydrogen atmosphere, and the time course of the reaction is analyzed by gas chromatography. The results for the decanoic acid modified catalyst are shown in FIG.
［効果〕
本触媒により、不均一触媒反応系では比較的困難とされ
ていた炭素−炭素二重結合と親水性官能基を有する脂肪
族化合物の二重結合の位置選択的接触水素添加反応が達
成でき、反応生成物と触媒との分離も容易である。[Effect] This catalyst achieves the regioselective catalytic hydrogenation reaction of carbon-carbon double bonds and double bonds of aliphatic compounds with hydrophilic functional groups, which was relatively difficult in heterogeneous catalytic reaction systems. It is also easy to separate the reaction product and catalyst.
図１はデカン酸修飾白金担持アルミナ触媒ニよる各種ヘ
キセノールの接触水素添加反応図２は白金担持アルミナ
（コントロール触媒）による各種ヘキセノールの接触水
素添加反応図３はデカン酸修飾白金担持アルミナ触媒に
よるトランス ２−ヘキセノールとトランス ４−ヘキ
セノールの共存下の接触水素添加反応図４は白金担持ア
ルミナ（コントロール触媒）によるトランス ２−ヘキ
セノールとトランス４−ヘキセノールの共存下の接触水
素添加反応図５はヘキサン酸修飾白金担持アルミナ触媒
によるトランス ２−ヘキセノールとトランス ４−ヘ
キセノールの共存下の接触水素添加反応図６はミリスチ
ン酸修飾白金担持アルミナ触媒によるトランス ２−ヘ
キセノールとトランス４−ヘキセノールの共存下の接触
水素添加反応図７はアジピン酸修飾白金担持アルミナ触
媒によるトランス ２−ヘキセノールとトランス ４−
ヘキセノールの共存下の接触水素添加反応図８は安息香
酸修飾白金担持アルミナ触媒によるトランス ２−ヘキ
セノールとトランス ４−ヘキセノールの共存下の接触
水素添加反応図９はデカン酸修飾白金担持アルミナ触媒
によるゲラニオールの接触水素添加反応
時 間 ／ ｈｒ
図
時間／ｈｒ
ヘキセ
９！ Ｉｖｌ ／ ｈｒ
０ トランス ２−ヘキセノール
０ トランス ４−−Ｓキセノール
時
間
／ｈｒ
図
トランス ２−へキセノ−９
トランス ４−へキセノ−１し
時間／ｈｒ
図
トランス ２−へキゼノール
トランス ４−へ午ゼノール
時間
／
ｒ
図
０ トランス ２−へキゼノール
０ トランス ４−へキゼノール
時間
／ｈｒ
図
トランス ２−へキゼノール
トランス ４−へ千七ノール
時間
図
／ｈｒ
時
閏
図
／
トランス
トランス
２〜へ午セ／−ノ１
４−へキセノ−２
大
Ｈ
手
続
補
正
書
（自発）
平成元年１λ月１１日Figure 1 shows the catalytic hydrogenation reaction of various types of hexenol using a decanoic acid-modified platinum-supported alumina catalyst. Figure 2 shows the catalytic hydrogenation reaction of various types of hexenol using a platinum-supported alumina (control catalyst). - Catalytic hydrogenation reaction in the coexistence of hexenol and trans 4-hexenol Figure 4 shows the catalytic hydrogenation reaction in the coexistence of trans 2-hexenol and trans 4-hexenol using platinum-supported alumina (control catalyst) Figure 5 shows hexanoic acid modified platinum Catalytic hydrogenation reaction in the coexistence of trans 2-hexenol and trans 4-hexenol using a supported alumina catalyst Figure 6 is a diagram of the catalytic hydrogenation reaction in the coexistence of trans 2-hexenol and trans 4-hexenol using a myristic acid modified platinum supported alumina catalyst. 7 is trans 2-hexenol and trans 4- by adipic acid modified platinum-supported alumina catalyst.
Catalytic hydrogenation reaction in the coexistence of hexenol Figure 8 shows the catalytic hydrogenation reaction in the coexistence of trans-2-hexenol and trans-4-hexenol using a benzoic acid-modified platinum-supported alumina catalyst. Catalytic hydrogenation reaction time / hr Figure time / hr Hexe9! Ivl / hr 0 trans 2-hexenol 0 trans 4-S xenol time/hr Fig. trans 2-hexenol-9 trans 4-hexeno-1 time/hr Fig. trans 2-hexenol trans 4-Hexenol Time/r Figure 0 Trans 2-Hexenol 0 Trans 4-Hexenol Time/hr Figure Transformer 2-Hexenol Trans 4-Hexenol Time Chart/hr Time Leap Chart/Trans Trans 2~Hexenol Time/hr No.1 4-Hexeno-2 Large H Procedural Amendment (Voluntary) 1989/1/11
Claims (1)
とする親水性官能基と炭素−炭素二重結合を有する脂肪
族化合物の水素添加用触媒。A catalyst for hydrogenation of aliphatic compounds having a hydrophilic functional group and a carbon-carbon double bond, characterized in that a carboxylic acid is adsorbed on platinum-supported alumina.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4020789A JPH02222728A (en) | 1989-02-22 | 1989-02-22 | Catalyst for positionally selective hydrogenation of carbon-carbon double bond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4020789A JPH02222728A (en) | 1989-02-22 | 1989-02-22 | Catalyst for positionally selective hydrogenation of carbon-carbon double bond |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02222728A true JPH02222728A (en) | 1990-09-05 |
Family
ID=12574335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4020789A Pending JPH02222728A (en) | 1989-02-22 | 1989-02-22 | Catalyst for positionally selective hydrogenation of carbon-carbon double bond |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02222728A (en) |
-
1989
- 1989-02-22 JP JP4020789A patent/JPH02222728A/en active Pending
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