JPS6230970B2 - - Google Patents
Info
- Publication number
- JPS6230970B2 JPS6230970B2 JP54160101A JP16010179A JPS6230970B2 JP S6230970 B2 JPS6230970 B2 JP S6230970B2 JP 54160101 A JP54160101 A JP 54160101A JP 16010179 A JP16010179 A JP 16010179A JP S6230970 B2 JPS6230970 B2 JP S6230970B2
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated
- reaction
- selectivity
- catalyst
- citral
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000003880 polar aprotic solvent Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 9
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 8
- 229940043350 citral Drugs 0.000 description 8
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 8
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 6
- 239000005792 Geraniol Substances 0.000 description 6
- -1 aromatic mercaptans Chemical class 0.000 description 6
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 6
- 229940113087 geraniol Drugs 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- 239000003570 air Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229930003633 citronellal Natural products 0.000 description 3
- 235000000983 citronellal Nutrition 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- 229910017752 Cu-Zn Inorganic materials 0.000 description 2
- 229910017813 Cu—Cr Inorganic materials 0.000 description 2
- 229910017943 Cu—Zn Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- BLUHKGOSFDHHGX-UHFFFAOYSA-N Phytol Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C=CO BLUHKGOSFDHHGX-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BOTWFXYSPFMFNR-OALUTQOASA-N all-rac-phytol Natural products CC(C)CCC[C@H](C)CCC[C@H](C)CCCC(C)=CCO BOTWFXYSPFMFNR-OALUTQOASA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YHRUHBBTQZKMEX-YFVJMOTDSA-N (2-trans,6-trans)-farnesal Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\C=O YHRUHBBTQZKMEX-YFVJMOTDSA-N 0.000 description 1
- CRDAMVZIKSXKFV-YFVJMOTDSA-N (2-trans,6-trans)-farnesol Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CO CRDAMVZIKSXKFV-YFVJMOTDSA-N 0.000 description 1
- YHRUHBBTQZKMEX-UHFFFAOYSA-N (2E,6E)-3,7,11-trimethyl-2,6,10-dodecatrien-1-al Natural products CC(C)=CCCC(C)=CCCC(C)=CC=O YHRUHBBTQZKMEX-UHFFFAOYSA-N 0.000 description 1
- VIINAUVGZZLXGK-WPZRUTIUSA-N (2z)-3,7-dimethylocta-2,6-dien-1-ol;(2e)-3,7-dimethylocta-2,6-dien-1-ol Chemical compound CC(C)=CCC\C(C)=C/CO.CC(C)=CCC\C(C)=C\CO VIINAUVGZZLXGK-WPZRUTIUSA-N 0.000 description 1
- 239000001707 (E,7R,11R)-3,7,11,15-tetramethylhexadec-2-en-1-ol Substances 0.000 description 1
- BOTWFXYSPFMFNR-HMMYKYKNSA-N (e)-3,7,11,15-tetramethylhexadec-2-en-1-ol Chemical compound CC(C)CCCC(C)CCCC(C)CCC\C(C)=C\CO BOTWFXYSPFMFNR-HMMYKYKNSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- 229930008411 3,7-dimethylocta-2,6-dien-1-ol Natural products 0.000 description 1
- YNWSTXBQNLCEPJ-UHFFFAOYSA-N 3-decyl-3h-dithiole Chemical compound CCCCCCCCCCC1SSC=C1 YNWSTXBQNLCEPJ-UHFFFAOYSA-N 0.000 description 1
- WRXOZRLZDJAYDR-UHFFFAOYSA-N 3-methylbenzenethiol Chemical compound CC1=CC=CC(S)=C1 WRXOZRLZDJAYDR-UHFFFAOYSA-N 0.000 description 1
- YHRUHBBTQZKMEX-FBXUGWQNSA-N E,E-Farnesal Natural products CC(C)=CCC\C(C)=C/CC\C(C)=C/C=O YHRUHBBTQZKMEX-FBXUGWQNSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HNZBNQYXWOLKBA-UHFFFAOYSA-N Tetrahydrofarnesol Natural products CC(C)CCCC(C)CCCC(C)=CCO HNZBNQYXWOLKBA-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003012 phosphoric acid amides Chemical class 0.000 description 1
- BOTWFXYSPFMFNR-PYDDKJGSSA-N phytol Chemical compound CC(C)CCC[C@@H](C)CCC[C@@H](C)CCC\C(C)=C\CO BOTWFXYSPFMFNR-PYDDKJGSSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- CRDAMVZIKSXKFV-UHFFFAOYSA-N trans-Farnesol Natural products CC(C)=CCCC(C)=CCCC(C)=CCO CRDAMVZIKSXKFV-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-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
Description
本発明は不飽和アルコールから不飽和アルデヒ
ド類の製造方法に関するものである。更に詳しく
説明すると、一般式
The present invention relates to a method for producing unsaturated aldehydes from unsaturated alcohols. To explain in more detail, the general formula
【式】
で表わされる不飽和アルコールを、芳香属メルカ
プタン類を触媒として、極性非プロトン溶媒を用
いて、酸素雰囲気下に反応させることを特徴とす
る一般式A general formula characterized by reacting an unsaturated alcohol represented by the formula with an aromatic mercaptan as a catalyst and a polar aprotic solvent in an oxygen atmosphere.
【式】で表わされ
る不飽和アルデヒドの製造方法〔式中、R1は水
素又は低級アルキル基を表わし、R2は飽和もし
くは不飽和の炭化水素基を表わす。〕に関するも
のである。
従来、不飽和アルコールから不飽和アルデヒド
類の製造方法には、
(1) 重クロム酸混液で酸化する方法、
(2) 活性MnO2と加熱酸化する方法、
(3) Cu、Agなどの金属又はこれらの合金を含む
固体触媒による接触空気酸化する方法、
(4) Cu―Zn、Cu―Cr、ZnOなどの固体触媒を用
いて脱水素する方法、
(5) Zn、In、Ta、Al、Gaなどの低融点金属又
は、これらの合金の溶融状物と接触させる方法
などがある。
重クロム酸混液で酸化する方法は、及び活性
MnO2による熱酸化する方法では多量の酸化剤を
消費する欠点があり、Cu、Agなどの金属又はこ
れらの合金を含む固体触媒による接触空気酸化す
る方法及びCu―Zn、Cu―Cr、ZnOなどの固体触
媒を用いて脱水素する方法によれば、高選択率で
得られる例もあるが、一般に固体触媒を用いる気
相反応では触媒の表層部の微細な構造などによつ
て反応結果が大きく左右されることが避け難く又
触媒の調製に特別の注意と熟練を要するという煩
雑さがある。又、Zn、In、Ta、Al、Gaなどの低
融点金属又はこれらの合金の溶融状物と接触させ
る方法では、数100℃の高温を要し、原料アルコ
ールは低濃度で接触時間を大きくとらなければな
らない処から、実用場面での操業効率は低く、不
飽和アルデヒドを得るには、いまだ低選択率であ
る。
本発明者らは、かかる従来の欠点を克服すべく
不飽和アルコールからの不飽和アルデヒド類の製
造方法を検討した結果、不飽和アルコールを芳香
族メルカプタン触媒を用いて酸素雰囲気下反応さ
せることにより不飽和アルデヒド類を比較的高選
択率で得ることを見い出し、本発明を完成した。
本発明で用いるメルカプタン類としては、ベンゼ
ンチオール、Ｏ，ｍ，Ｐ―トルエンチオール、ク
ロロチオフエノール等に代表される無置換及び／
又は置換芳香族メルカプタン類を例示することが
できる。ここで、オクチルメルカプタン、デシル
メルカプタン等に代表されるアルキルメルカプタ
ン類、ジチオグリコール、デシルジチオール等に
代表されるアルキルジチオール類、その他チオグ
リコール酸、メルカプトエタノールの如きメルカ
プタン類を使用した場合は、不飽和アルコールの
転化率の上昇につれて選択率の低下が見られ好ま
しくない。
本発明で用いることができる芳香族メルカプタ
ン類は、容易にかつ安価に入手しうる触媒であつ
て反応後触媒の分離再使用が簡単な操作で出来る
という特徴を有し、工業的価値はきわめて高い。
本発明に用いるかかる不飽和アルコールの具体
例としては、ゲラニオール・ネロール（３，７―
ジメチル―２，６―オクタジエン―１―オー
ル）、アアルネソール（３，７，11―トリメチル
―２，６，10―ドデカトリエン―１―オール）、
フイトール（３，７，11，15―テトラメチル―２
―ヘキサデセン―１―オール）等を例示すること
ができる。本発明で得られる不飽和アルデヒド類
としては、シトラール、フアルネサール、フイチ
ルアルデヒド等が例示できる。いずれのアルデヒ
ドも香料工業において重要な物質であり、香料と
してあるいは香料の合成中間原料、溶剤または保
留剤として用いられる。またこれらのアルデヒド
類は医薬や農薬の合成中間原料として有用な化合
物であり、例えばシトラールはビタミンＡの合成
中間体として重要である。
本発明に用いる触媒の使用量は、原料不飽和ア
ルコールに対し0.5〜100重量パーセントの範囲が
好ましく、特に１〜50重量パーセントの範囲が良
い。触媒の使用量が50重量％以上になると経済的
な見地から、又0.5重量％以下になると反応の進
行が遅くなり好ましくない。
反応雰囲気は、酸素雰囲気にすることが必要で
あり、酸素、空気または酸素富化空気を使用する
ことができる。
本発明の特徴として特定の溶媒を用いることが
必要である。特定の溶媒としては、Ｎ，Ｎ―ジメ
チルホルムアミド（DMF）、Ｎ，Ｎ―ジエチルホ
ルムアミド（DEF）、Ｎ，Ｎ―ジメチルアセトア
ミド（DMA）等の酸アミド類、ジメチルスルホ
キシド（DMSO）、テトラメチレンスルホン（ス
ルホラン）等の含イオウ化合物、テトラメチル尿
素等の尿素系化合物、ヘキサメチルホスホルアミ
ド等のリン酸アミドなどに代表される誘電率の高
い一般に極性非プロトン溶媒と呼ばれているもの
である。又、ピリジン及びピリジン誘導体も有効
である。しかし、一般に溶媒として用いられる炭
化水素類、エーテル類、エステル類や、その他ニ
トロ化合物、ニトリル類などでは本反応に対する
効果は小さくなる。反応温度は20℃から200℃の
範囲がよく、特に40℃〜150℃の範囲が好まし
い。反応終了後は単蒸留又は希アルカリ水溶液等
による化学的分離操作により触媒を分離した後、
蒸留又は亜硫酸ソーダなどの付加剤を用いて生成
物と未反応原料を分離することができる。以下に
実施例を挙げて本発明方法を詳細に説明する。
実施例 １
ゲラニオール20ｇとネロール10ｇの混合液にチ
オフエノール1.5ｇとＮ，Ｎ―ジメチルホルムア
ミド（DMF）60ｇを加え、酸素雰囲気下に於て
80℃で１時間15分撹拌させた。反応液は、ガスク
ロマトグラフイーにより分析を行つた結果、ゲラ
ニオール・ネロール混合物の転化率は30％であ
り、生成したシトラールの選択率は81％であり、
副生物としてシトロネラールが選択率で７％得ら
れた。
比較例 １
実施例１に於て、チオフエノールを３ｇとし無
溶媒で60℃１時間撹拌した他は、実施例１と同様
に反応を行つた結果、ゲラニオール・ネロール混
合物の転化率は、29％であり、生成したシトラー
ルの選択率は14％であつた。
実施例 ２
実施例１に於て、触媒をｍ―トルエンチオール
にした他は実施例１と同様に反応を行つた結果、
ゲラニオール・ネロール混合物の転化率は27％で
あり、生成したシトラールの選択率は72％であ
り、シトロネラールの選択率は８％であつた。
実施例 ３〜６
実施例１に於て、溶媒の種類及びその他の条件
を表１に掲げる条件に変え他は実施例１と同様に
反応を行い表１の結果を得た。A method for producing an unsaturated aldehyde represented by the formula [In the formula, R 1 represents hydrogen or a lower alkyl group, and R 2 represents a saturated or unsaturated hydrocarbon group. ]. Conventionally, methods for producing unsaturated aldehydes from unsaturated alcohols include (1) oxidation with a dichromic acid mixture, (2) heating oxidation with active MnO 2 , (3) oxidation with metals such as Cu, Ag, or (4) Dehydrogenation method using solid catalysts such as Cu-Zn, Cu-Cr, ZnO, etc. (5) Zn, In, Ta, Al, Ga There is a method of contacting with a molten material of a low melting point metal such as or an alloy thereof. The method of oxidizing with dichromic acid mixture is
The method of thermal oxidation using MnO 2 has the disadvantage of consuming a large amount of oxidizing agent, and the method of catalytic air oxidation using a solid catalyst containing metals such as Cu and Ag or their alloys, and the method of catalytic air oxidation using Cu-Zn, Cu-Cr, ZnO, etc. Dehydrogenation methods using solid catalysts can achieve high selectivity in some cases, but gas phase reactions that use solid catalysts generally have a large reaction result due to the fine structure of the surface layer of the catalyst. There is a complication in that the preparation of the catalyst requires special care and skill. In addition, the method of contacting with a melt of low melting point metals such as Zn, In, Ta, Al, Ga, or their alloys requires a high temperature of several hundred degrees Celsius, and the raw alcohol has a low concentration and a long contact time. As a result, the operational efficiency in practical situations is low, and the selectivity for obtaining unsaturated aldehydes is still low. In order to overcome these conventional drawbacks, the present inventors investigated a method for producing unsaturated aldehydes from unsaturated alcohols, and found that unsaturated alcohols are reacted with aromatic mercaptan catalysts in an oxygen atmosphere. The present invention was completed by discovering that saturated aldehydes can be obtained with relatively high selectivity.
Examples of mercaptans used in the present invention include unsubstituted and/or
Or substituted aromatic mercaptans can be exemplified. When using alkyl mercaptans such as octyl mercaptan and decyl mercaptan, alkyl dithiols such as dithioglycol and decyl dithiol, and other mercaptans such as thioglycolic acid and mercaptoethanol, unsaturated As the alcohol conversion rate increases, the selectivity decreases, which is undesirable. The aromatic mercaptans that can be used in the present invention are catalysts that can be easily and inexpensively obtained, and the catalyst can be separated and reused after the reaction with a simple operation, and has extremely high industrial value. . Specific examples of such unsaturated alcohols used in the present invention include geraniol and nerol (3,7-
dimethyl-2,6-octadien-1-ol), aarnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol),
Phytol (3,7,11,15-tetramethyl-2
-hexadecen-1-ol). Examples of the unsaturated aldehydes obtained in the present invention include citral, farnesal, and phythylaldehyde. All aldehydes are important substances in the fragrance industry and are used as fragrances, intermediate raw materials for synthesis of fragrances, solvents, or preservatives. Further, these aldehydes are compounds useful as intermediate raw materials for the synthesis of medicines and agricultural chemicals. For example, citral is important as an intermediate for the synthesis of vitamin A. The amount of the catalyst used in the present invention is preferably in the range of 0.5 to 100% by weight, particularly preferably in the range of 1 to 50% by weight, based on the raw unsaturated alcohol. If the amount of catalyst used is more than 50% by weight, it is not preferable from an economical point of view, and if it is less than 0.5% by weight, the progress of the reaction will be slowed down, which is undesirable. The reaction atmosphere needs to be an oxygen atmosphere, and oxygen, air or oxygen-enriched air can be used. As a feature of the present invention, it is necessary to use a specific solvent. Specific solvents include acid amides such as N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), and N,N-dimethylacetamide (DMA), dimethylsulfoxide (DMSO), and tetramethylene sulfone. These are generally called polar aprotic solvents with high dielectric constants, such as sulfur-containing compounds such as (sulfolane), urea compounds such as tetramethylurea, and phosphoric acid amides such as hexamethylphosphoramide. . Pyridine and pyridine derivatives are also effective. However, hydrocarbons, ethers, esters, and other nitro compounds, nitrites, etc., which are generally used as solvents, have a small effect on this reaction. The reaction temperature is preferably in the range of 20°C to 200°C, particularly preferably in the range of 40°C to 150°C. After the reaction is completed, the catalyst is separated by simple distillation or chemical separation using a dilute aqueous alkaline solution, etc.
Product and unreacted materials can be separated using distillation or an additive such as sodium sulfite. The method of the present invention will be explained in detail with reference to Examples below. Example 1 1.5 g of thiophenol and 60 g of N,N-dimethylformamide (DMF) were added to a mixed solution of 20 g of geraniol and 10 g of nerol, and the mixture was heated under an oxygen atmosphere.
The mixture was stirred at 80°C for 1 hour and 15 minutes. The reaction solution was analyzed by gas chromatography, and the conversion rate of the geraniol/nerol mixture was 30%, and the selectivity of the produced citral was 81%.
Citronellal was obtained as a by-product with a selectivity of 7%. Comparative Example 1 The reaction was carried out in the same manner as in Example 1, except that 3 g of thiophenol was used and stirred for 1 hour at 60°C without a solvent. As a result, the conversion rate of the geraniol/nerol mixture was 29%. The selectivity of the produced citral was 14%. Example 2 The reaction was carried out in the same manner as in Example 1 except that m-toluenethiol was used as the catalyst. As a result,
The conversion rate of the geraniol-nerol mixture was 27%, the selectivity of the produced citral was 72%, and the selectivity of citronellal was 8%. Examples 3 to 6 In Example 1, except that the type of solvent and other conditions were changed to those listed in Table 1, the reaction was carried out in the same manner as in Example 1, and the results shown in Table 1 were obtained.
【表】
実施例 ７
実施例１に於て、原料をネロールとし、60℃で
２時間40分とした他は実施例１と同様に反応を行
つた結果、ネロールの転化率は77％、生成ゲラニ
オールの選択率は30％、生成シトラールの選択率
は44％であつた。即ち、不飽和アルコールの転化
率は46％であり、消費不飽和アルコールからのシ
トラールの選択率は76％であつた。
実施例 ８
実施例１に於て、反応雰囲気を空気気流中と
し、２時間30分とした他は実施例１と同様に反応
を行つた結果、ゲラニオール・ネロール転化率は
28％であり、シトラール選択率は50％であり、シ
トロネラールの選択率は45％であつた。[Table] Example 7 In Example 1, the reaction was carried out in the same manner as in Example 1 except that the raw material was nerol and the temperature was 60°C for 2 hours and 40 minutes. As a result, the conversion rate of nerol was 77%, and the reaction was The selectivity for geraniol was 30%, and the selectivity for citral produced was 44%. That is, the conversion rate of unsaturated alcohol was 46%, and the selectivity of citral from the consumed unsaturated alcohol was 76%. Example 8 The reaction was carried out in the same manner as in Example 1, except that the reaction atmosphere was an air stream and the reaction time was 2 hours and 30 minutes. As a result, the conversion rate of geraniol and nerol was as follows.
The selectivity for citral was 50% and the selectivity for citronellal was 45%.
Claims (1)
タン類を触媒として極性非プロトン溶媒を用い
て、酸素雰囲気下に反応させることを特徴とす
る。 一般式 で表わされる不飽和アルデヒドの製造方法。 〔式中、R1は水素又は低級アルキル基を表わ
し、R2は飽和もしくは不飽和炭化水素基を表わ
す。〕[Claims] 1. General formula It is characterized by reacting an unsaturated alcohol represented by the following in an oxygen atmosphere using an aromatic mercaptan as a catalyst and a polar aprotic solvent. general formula A method for producing an unsaturated aldehyde represented by [In the formula, R 1 represents hydrogen or a lower alkyl group, and R 2 represents a saturated or unsaturated hydrocarbon group. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16010179A JPS5683435A (en) | 1979-12-10 | 1979-12-10 | Preparation of unsaturated aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16010179A JPS5683435A (en) | 1979-12-10 | 1979-12-10 | Preparation of unsaturated aldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5683435A JPS5683435A (en) | 1981-07-08 |
| JPS6230970B2 true JPS6230970B2 (en) | 1987-07-06 |
Family
ID=15707865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16010179A Granted JPS5683435A (en) | 1979-12-10 | 1979-12-10 | Preparation of unsaturated aldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5683435A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7604277B2 (en) | 2005-12-28 | 2009-10-20 | Yanmar Co., Ltd. | Working vehicle equipped with assist grip |
| CN101128341B (en) | 2005-12-28 | 2010-08-25 | 洋马株式会社 | Tractor |
-
1979
- 1979-12-10 JP JP16010179A patent/JPS5683435A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5683435A (en) | 1981-07-08 |
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