JPH0213651B2 - - Google Patents
Info
- Publication number
- JPH0213651B2 JPH0213651B2 JP57190570A JP19057082A JPH0213651B2 JP H0213651 B2 JPH0213651 B2 JP H0213651B2 JP 57190570 A JP57190570 A JP 57190570A JP 19057082 A JP19057082 A JP 19057082A JP H0213651 B2 JPH0213651 B2 JP H0213651B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- octadien
- octen
- catalysts
- isomerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 22
- PCELKVAQHUEQKH-UHFFFAOYSA-N octa-1,7-dien-3-ol Chemical compound C=CC(O)CCCC=C PCELKVAQHUEQKH-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 18
- GFLKFABQDSYXTM-UHFFFAOYSA-N oct-7-en-3-one Chemical compound CCC(=O)CCCC=C GFLKFABQDSYXTM-UHFFFAOYSA-N 0.000 description 12
- 238000006317 isomerization reaction Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 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
- LJFCDOMDEACIMM-UHFFFAOYSA-N zinc chromium(3+) oxygen(2-) Chemical compound [O-2].[Cr+3].[Zn+2] LJFCDOMDEACIMM-UHFFFAOYSA-N 0.000 description 2
- KLBAYHDGSRBDKN-VOTSOKGWSA-N (4e)-octa-1,4-dien-3-one Chemical compound CCC\C=C\C(=O)C=C KLBAYHDGSRBDKN-VOTSOKGWSA-N 0.000 description 1
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- VODBHXZOIQDDST-UHFFFAOYSA-N copper zinc oxygen(2-) Chemical compound [O--].[O--].[Cu++].[Zn++] VODBHXZOIQDDST-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVNHCNIXIDWVRO-UHFFFAOYSA-N oct-7-en-3-ol Chemical compound CCC(O)CCCC=C TVNHCNIXIDWVRO-UHFFFAOYSA-N 0.000 description 1
- WZYUJMCDCAFUKD-UHFFFAOYSA-N octa-1,3-dien-3-ol Chemical compound CCCCC=C(O)C=C WZYUJMCDCAFUKD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- -1 saturated alicyclic hydrocarbons Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は１，７−オクタジエン−３−オールの
異性化による７−オクテン−３−オンの製造方法
に関する。
７−オクテン−３−オンは反応性に富む末端ビ
ニル基およびカルボニル基を有していることから
医薬、農薬、香料などの出発原料として極めて有
用であり、たとえば生理活性を有するｌ−３−ヒ
ドロキシデカン酸の原料として用いられることが
知られている。しかし、これまでその有利な製造
法が開発されていないこともあり、７−オクテン
−３−オンは工業的規模で生産されるには至つて
いない。
先に本発明者らはブタジエンと水とをパラジウ
ム触媒の存在下で反応させることにより１，７−
オクタジエン−３−オールを工業的に有利に製造
しうることを見出した（特開昭56−138129号公報
および特開昭57−123129号公報参照）。本発明者
らはかかる背景から１，７−オクタジエン−３−
オールを出発原料とする工業的実施に適した７−
オクテン−３−オンの製造方法を開発すべく鋭意
検討を行なつた。その結果、１，７−オクタジエ
ン−３−オールを銅、クロムおよび亜鉛から選ば
れる金属の少くとも二種の組合せからなる金属酸
化物触媒の存在下に反応させるとアリル位の二重
結合のみが選択的に異性化した化合物である７−
オクテン−３−オンが高収率で生成することを見
出し、本発明を完成するに至つた。
本発明の方法において使用される銅、クロムお
よび亜鉛から選ばれる金属の少くとも二種の組合
せからなる金属酸化物触媒としては、銅亜鉛酸化
物、銅クロム酸化物、亜鉛クロム酸化物、銅−亜
鉛−クロム酸化物などを例示することができる。
前記の金属酸化物触媒は一般に脱水素反応の触媒
として工業的にも汎用され、商業生産されており
容易に入手することができるほか、たとえば触媒
工学講座10元素別触媒便覧90〜92頁および365〜
367頁（昭和42年２月25日株式会社地人書館発
行）、Ind.Eng.Chem.、20 694（1928）などに記
載されている種々の方法に従つて製造することも
できる。これらの触媒はタングステン、モリブデ
ン、レニウム、マグネシウム、カルシウム、ジル
コニウム、マンガン、チタン、鉄、バリウムなど
から選ばれる他の金属成分で部分的に変性されて
いてもよい。また触媒はアルミナ、シリカ、ケイ
ソウ土などの担体に担持されているものを使用す
ることもできる。これらの触媒はそれぞれ単独で
用いてもよく、二種またはそれ以上を組合せて用
いてもよい。触媒はその使用に先立ち予め水素処
理すると触媒活性が向上する場合がある。反応を
液相で実施する場合、触媒は金属換算で反応混合
液に対して0.1〜20重量パーセントの割合で用い
られる。なお異性化および水添触媒として一般に
汎用なパラジウム触媒、ニツケル触媒、コバルト
触媒、ロジウム触媒、白金触媒などを用いて１，
７−オクタジエン−３−オールの異性化反応を実
施した場合には、７−オクテン−３−オンの生成
割合が低く、７−オクテン−３−オンとの分離が
実質的に不可能な多数の副生成物が多量に生成す
るので、これら汎用の触媒は１，７−オクタジエ
ン−３−オールの異性化による７−オクテン−３
−オンの生成反応には使用し得ない。
本発明の方法にしたがう１，７−オクタジエン
−３−オールの異性化反応は好ましくは窒素ガ
ス、炭酸ガス、ヘリウムガス、アルゴンガスなど
の反応条件下で不活性なガスの雰囲気下で行なわ
れるが、不活性ガスの一部を水素ガスに置き換え
てもよい。ただし、水素ガスの共存下で反応を行
なう場合には、水素ガスの分圧を１気圧以下に留
めた方がよい。水素ガスの分圧が１気圧を越える
と水添反応の割合が増大し、７−オクテン−３−
オンの選択率が低下するので好ましくない。反応
温度は130〜300℃、好ましくは150〜250℃の範囲
から選ばれる。反応は撹拌型反応槽、気泡塔型反
応槽あるいは充填塔型反応槽中で液槽または気相
において連続方式またはバツチ方式で実施するこ
とができる。反応を液相で実施する場合、原料で
ある１，７−オクタジエン−３−オールまたは生
成物である７−オクテン−３−オンに溶媒として
の機能を兼ねさせることができる。また反応条件
下において不活性な他の有機溶媒を用いて行なう
こともできる。使用可能な有機溶媒としては、ヘ
キサン、オクタン、デカン、流動パラフインなど
の飽和脂肪族炭化水素類、シクロヘキサン、メチ
ルシクロヘキサンなどの飽和脂環式炭化水素類、
ベンゼン、トルエン、キシレン、ビフエニルなど
の芳香族炭化水素類、ジイソプロピルエーテル、
ジブチルエーテル、ジオクチルエーテル、ジフエ
ニルエーテル、テトラヒドロフラン、ジエチレン
グリコールジエチルエーテル、ポリエチレングリ
コールジメチルエーテルなどのエーテル類、エタ
ノール、ブタノール、オクタノール、エチレング
リコール、グリセリン、ポリエチレングリコール
などのアルコール類、などを挙げることができ
る。
本発明の方法により生成する７−オクテン−３
−オンは反応原料の１，７−オクタジエン−３−
オールより低沸点であるので、７−オクテン−３
−オンを反応系外に留出させながら反応を行なう
こと（反応蒸留方式）は本発明の方法の特に望ま
しい実施態様の１つであり、これにより副生物の
生成が一層抑制される。反応で生成する７−オク
テン−３−オンは反応混合液または留出液から通
常の蒸留操作によつて取得することができる。
本発明の方法に従う反応において、水を原料で
ある１，７−オクタジエン−３−オールに対して
飽和溶解度以下の量で共存させることにより低沸
点化合物の副生を抑制することもできる。また、
反応混合液から蒸留操作により７−オクテン−３
−オンを留出させたあとの残留液を前記金属酸化
物触媒の存在下に再度反応させると副生成物の大
半が目的物である７−オクテン−３−オンに変換
されるので、反応の選択率が一層向上する。
以下、実施例により本発明の方法を具体的に説
明する。
実施例 １
撹拌装置、液およびガスフイード口、留出液冷
却装置を備えた内容100mlの三つ口フラスコに粉
末状銅クロム酸化物触媒（日揮化学社製N203：
CuO−Cr2O3、MnO25％）2.0ｇおよび流動パラ
フイン20mlを仕込み、フラスコを230℃に保持さ
れたオイルバスを用いて外部加熱した。激しく撹
拌しながら、窒素ガスを25／hrの速度で流通さ
せつつ、１，７−オクタジエン−３−オールを
200ml／hrの速度で定量フイードポンプを利用す
ることによつて連続的に供給した。このような要
領で合計８時間にわたつて１，７−オクタジエン
−３−オールの異性化（蒸留）反応を行なつた。
毎時約200mlの留出液が得られ、反応を通じてフ
ラスコ内の液量は約20mlに保たれていた。８時間
の反応により合計1550mlの留出液が取得された。
ガスクロマトグラフイーによる分析から留出液中
には未反応の１，７−オクタジエン−３−オール
が13.5モル％、７−オクタノン2.6モル％、オク
タジエン−３−オン10.9モル％、オクタジエン
2.5モル％、７−オクテン−３−オンが70.5モル
％含まれていることがわかつた。この留出液1.0
Kgを理論段数40段の蒸留塔を用いて精留したとこ
ろ60〜61℃／10mmHgの留分として７−オクテン
−３−オンが約700ｇ（純度98％）得られた。
実施例２〜４および比較例１〜２
触媒の種類および量を変化させた以外は実施例
１と同様にして１，７−オクタジエン−３−オー
ルの異性化反応を行なつた。反応結果を表１に示
す。なお、表１において７−オクテン−３−オン
への異性化率は仕込み１，７−オクタジエン−３
−オールに対する留出液中の７−オクテン−３−
オンの割合（モル％）で示した。
The present invention relates to a process for producing 7-octen-3-one by isomerization of 1,7-octadien-3-ol. Since 7-octen-3-one has highly reactive terminal vinyl and carbonyl groups, it is extremely useful as a starting material for medicines, agricultural chemicals, fragrances, etc. It is known to be used as a raw material for decanoic acid. However, 7-octen-3-one has not yet been produced on an industrial scale, partly because an advantageous method for its production has not yet been developed. Previously, the present inventors reacted butadiene and water in the presence of a palladium catalyst to produce 1,7-
It has been found that octadien-3-ol can be produced industrially advantageously (see JP-A-56-138129 and JP-A-57-123129). Based on this background, the present inventors have determined that 1,7-octadiene-3-
7- suitable for industrial implementation using oars as starting material
We conducted extensive research to develop a method for producing octen-3-one. As a result, when 1,7-octadien-3-ol is reacted in the presence of a metal oxide catalyst consisting of a combination of at least two metals selected from copper, chromium, and zinc, only the double bond at the allylic position is removed. 7- which is a selectively isomerized compound
It was discovered that octen-3-one can be produced in high yield, and the present invention was completed. The metal oxide catalyst consisting of a combination of at least two metals selected from copper, chromium and zinc used in the method of the present invention includes copper zinc oxide, copper chromium oxide, zinc chromium oxide, copper- Examples include zinc-chromium oxide.
The metal oxide catalysts mentioned above are generally used industrially as catalysts for dehydrogenation reactions, are commercially produced, and are easily available. ~
It can also be produced according to various methods described in Ind.Eng.Chem., 20 694 (1928), p. 367 (February 25, 1967, published by Jijinshokan Co., Ltd.). These catalysts may be partially modified with other metal components selected from tungsten, molybdenum, rhenium, magnesium, calcium, zirconium, manganese, titanium, iron, barium, and the like. Further, a catalyst supported on a carrier such as alumina, silica, diatomaceous earth, etc. can also be used. These catalysts may be used alone or in combination of two or more. Catalyst activity may be improved if the catalyst is previously treated with hydrogen prior to use. When the reaction is carried out in the liquid phase, the catalyst is used in an amount of 0.1 to 20 weight percent based on the reaction mixture in terms of metal. In addition, general-purpose palladium catalysts, nickel catalysts, cobalt catalysts, rhodium catalysts, platinum catalysts, etc. are used as isomerization and hydrogenation catalysts.
When the isomerization reaction of 7-octadien-3-ol is carried out, the production rate of 7-octen-3-one is low, and a large number of 7-octen-3-ones are produced, which is virtually impossible to separate from 7-octen-3-one. Since large amounts of by-products are produced, these general-purpose catalysts are not suitable for the isomerization of 7-octene-3-ol by the isomerization of 1,7-octadien-3-ol.
It cannot be used in -one production reactions. The isomerization reaction of 1,7-octadien-3-ol according to the method of the present invention is preferably carried out under an inert gas atmosphere under reaction conditions such as nitrogen gas, carbon dioxide gas, helium gas, argon gas, etc. , a portion of the inert gas may be replaced with hydrogen gas. However, when the reaction is carried out in the presence of hydrogen gas, it is better to keep the partial pressure of hydrogen gas at 1 atmosphere or less. When the partial pressure of hydrogen gas exceeds 1 atm, the rate of hydrogenation reaction increases, and 7-octene-3-
This is not preferable because the on selectivity decreases. The reaction temperature is selected from the range of 130 to 300°C, preferably 150 to 250°C. The reaction can be carried out in a stirred reactor, a bubble column reactor or a packed column reactor, in a liquid bath or in the gas phase, in a continuous mode or in a batch mode. When the reaction is carried out in a liquid phase, the raw material 1,7-octadien-3-ol or the product 7-octen-3-one can also function as a solvent. It is also possible to use other organic solvents that are inert under the reaction conditions. Usable organic solvents include saturated aliphatic hydrocarbons such as hexane, octane, decane, and liquid paraffin; saturated alicyclic hydrocarbons such as cyclohexane and methylcyclohexane;
Aromatic hydrocarbons such as benzene, toluene, xylene, and biphenyl, diisopropyl ether,
Examples include ethers such as dibutyl ether, dioctyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol diethyl ether, and polyethylene glycol dimethyl ether, and alcohols such as ethanol, butanol, octanol, ethylene glycol, glycerin, and polyethylene glycol. 7-octene-3 produced by the method of the present invention
-one is the reaction raw material 1,7-octadiene-3-
Since it has a lower boiling point than ol, 7-octene-3
Conducting the reaction while distilling the -one out of the reaction system (reactive distillation method) is one of the particularly desirable embodiments of the method of the present invention, and this further suppresses the production of by-products. 7-octen-3-one produced in the reaction can be obtained from the reaction mixture or distillate by conventional distillation operations. In the reaction according to the method of the present invention, the by-product of low-boiling compounds can be suppressed by coexisting water in an amount less than the saturation solubility of 1,7-octadien-3-ol as a raw material. Also,
7-octene-3 is obtained from the reaction mixture by distillation.
When the residual liquid after distilling off -one is reacted again in the presence of the metal oxide catalyst, most of the by-products are converted to the target product, 7-octen-3-one, so the reaction proceeds. Selectivity is further improved. Hereinafter, the method of the present invention will be specifically explained with reference to Examples. Example 1 A powdered copper chromium oxide catalyst (N203 manufactured by JGC Chemical Co., Ltd.:
2.0 g of CuO-Cr 2 O 3 , MnO 2 5%) and 20 ml of liquid paraffin were charged, and the flask was externally heated using an oil bath maintained at 230°C. While stirring vigorously and flowing nitrogen gas at a rate of 25/hr, 1,7-octadien-3-ol was added.
It was fed continuously by utilizing a metering feed pump at a rate of 200 ml/hr. The isomerization (distillation) reaction of 1,7-octadien-3-ol was carried out in this manner for a total of 8 hours.
Approximately 200 ml of distillate was obtained per hour, and the liquid volume in the flask was maintained at approximately 20 ml throughout the reaction. A total of 1550 ml of distillate was obtained after 8 hours of reaction.
Analysis by gas chromatography revealed that the distillate contained 13.5 mol% of unreacted 1,7-octadien-3-ol, 2.6 mol% of 7-octanone, 10.9 mol% of octadien-3-one, and octadiene.
It was found that 2.5 mol% and 70.5 mol% of 7-octen-3-one were contained. This distillate 1.0
When Kg was rectified using a distillation column with 40 theoretical plates, about 700 g of 7-octen-3-one (purity 98%) was obtained as a fraction at 60-61°C/10 mmHg. Examples 2 to 4 and Comparative Examples 1 to 2 The isomerization reaction of 1,7-octadien-3-ol was carried out in the same manner as in Example 1, except that the type and amount of the catalyst were changed. The reaction results are shown in Table 1. In addition, in Table 1, the isomerization rate to 7-octen-3-one is
-7-octene-3- in the distillate relative to the ol
It is expressed as a percentage of on (mol%).
【表】
様シーシーアイ社
製C−72)
[Table] C-72 manufactured by CCI Corporation)
Claims (1)
ロムおよび亜鉛から選ばれる金属の少くとも二種
の組合せからなる金属酸化物触媒の存在下に異性
化することを特徴とする７−オクテン−３−オン
の製造方法。1 7-octene-3, characterized in that 1,7-octadien-3-ol is isomerized in the presence of a metal oxide catalyst consisting of a combination of at least two metals selected from copper, chromium and zinc. -Method for manufacturing on.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57190570A JPS5978140A (en) | 1982-10-28 | 1982-10-28 | Preparation of 7-octen-3-one |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57190570A JPS5978140A (en) | 1982-10-28 | 1982-10-28 | Preparation of 7-octen-3-one |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5978140A JPS5978140A (en) | 1984-05-04 |
| JPH0213651B2 true JPH0213651B2 (en) | 1990-04-04 |
Family
ID=16260259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57190570A Granted JPS5978140A (en) | 1982-10-28 | 1982-10-28 | Preparation of 7-octen-3-one |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5978140A (en) |
-
1982
- 1982-10-28 JP JP57190570A patent/JPS5978140A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5978140A (en) | 1984-05-04 |
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