JPH09227439A - Aldehyde formation - Google Patents
Aldehyde formationInfo
- Publication number
- JPH09227439A JPH09227439A JP8075107A JP7510796A JPH09227439A JP H09227439 A JPH09227439 A JP H09227439A JP 8075107 A JP8075107 A JP 8075107A JP 7510796 A JP7510796 A JP 7510796A JP H09227439 A JPH09227439 A JP H09227439A
- Authority
- JP
- Japan
- Prior art keywords
- triflate
- aldehyde
- compound
- carbon monoxide
- reaction
- 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
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 5
- 230000015572 biosynthetic process Effects 0.000 title description 2
- -1 trifluoromethanesulfonic acid ester Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052990 silicon hydride Inorganic materials 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000002243 precursor Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTKHQYWRGFZFHG-UHFFFAOYSA-N trioctylsilicon Chemical compound CCCCCCCC[Si](CCCCCCCC)CCCCCCCC QTKHQYWRGFZFHG-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- REJDZFBNBHWURH-UHFFFAOYSA-N hexane;trifluoromethanesulfonic acid Chemical compound CCCCCC.OS(=O)(=O)C(F)(F)F REJDZFBNBHWURH-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910000083 tin tetrahydride Inorganic materials 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- DBXSBUOTVXRWEE-UHFFFAOYSA-N C1C=CCC1.FC(S(=O)(=O)O)(F)F Chemical compound C1C=CCC1.FC(S(=O)(=O)O)(F)F DBXSBUOTVXRWEE-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001503 aryl iodides Chemical class 0.000 description 1
- XBDIHYUIPCPRGX-UHFFFAOYSA-N butane;trifluoromethanesulfonic acid Chemical compound CCCC.OS(=O)(=O)C(F)(F)F XBDIHYUIPCPRGX-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- WVSCRRLWRRANJY-UHFFFAOYSA-N cyclohexen-1-yl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CCCCC1 WVSCRRLWRRANJY-UHFFFAOYSA-N 0.000 description 1
- LAUXCHIFWWAXRN-UHFFFAOYSA-N cyclohexene;trifluoromethanesulfonic acid Chemical compound C1CCC=CC1.OS(=O)(=O)C(F)(F)F LAUXCHIFWWAXRN-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GHXZPUGJZVBLGC-UHFFFAOYSA-N iodoethene Chemical compound IC=C GHXZPUGJZVBLGC-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WQWUQDVFRYMMCY-UHFFFAOYSA-N naphthalen-1-yl trifluoromethanesulfonate Chemical compound C1=CC=C2C(OS(=O)(=O)C(F)(F)F)=CC=CC2=C1 WQWUQDVFRYMMCY-UHFFFAOYSA-N 0.000 description 1
- MDWRQYBWVTXIIJ-UHFFFAOYSA-N naphthalen-2-yl trifluoromethanesulfonate Chemical compound C1=CC=CC2=CC(OS(=O)(=O)C(F)(F)F)=CC=C21 MDWRQYBWVTXIIJ-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- FDCPOHSUCCRXSV-UHFFFAOYSA-N octane;trifluoromethanesulfonic acid Chemical compound CCCCCCCC.OS(=O)(=O)C(F)(F)F FDCPOHSUCCRXSV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- BDFHUTZCIASNMZ-UHFFFAOYSA-N pentane trifluoromethanesulfonic acid Chemical compound FC(S(=O)(=O)O)(F)F.CCCCC BDFHUTZCIASNMZ-UHFFFAOYSA-N 0.000 description 1
- GRJHONXDTNBDTC-UHFFFAOYSA-N phenyl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=CC=C1 GRJHONXDTNBDTC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ISEIIPDWJVGTQS-UHFFFAOYSA-N tributylsilicon Chemical compound CCCC[Si](CCCC)CCCC ISEIIPDWJVGTQS-UHFFFAOYSA-N 0.000 description 1
- ISPSHPOFLYFIRR-UHFFFAOYSA-N trihexylsilicon Chemical compound CCCCCC[Si](CCCCCC)CCCCCC ISPSHPOFLYFIRR-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
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は有機化合物における化
学反応殊に、アルデヒド化の方法に関するものであり、
従って有機化合物にアルデヒド基を導入するときに広範
に利用することができるものである。FIELD OF THE INVENTION The present invention relates to a chemical reaction in an organic compound, particularly to a method for aldehyde formation,
Therefore, it can be widely used when introducing an aldehyde group into an organic compound.
【０００２】[0002]
【従来技術】一酸化炭素を炭素源として、芳香族炭化水
素にアルデヒド基を導入する方法として著名な方法にガ
ッターマンーコッホ法がある。この方法では高圧反応で
の収率は良好であるが、常圧での反応収率は低い。ま
た、一酸化炭素と水素及びコバルト触媒を使用して不飽
和化合物を還元的に末端アルデヒド化する方法もある。
コバルトカルボニル化合物の毒性が指摘されている。2. Description of the Related Art The Gattermann-Koch method is a well-known method for introducing an aldehyde group into an aromatic hydrocarbon using carbon monoxide as a carbon source. In this method, the yield in the high pressure reaction is good, but the yield in the normal pressure is low. There is also a method of reductively converting the unsaturated compound into a terminal aldehyde using carbon monoxide, hydrogen and a cobalt catalyst.
The toxicity of cobalt carbonyl compounds has been pointed out.
【０００３】有機ハロゲン化化合物を触媒の存在下、一
酸化炭素と水素化スズを使用してアルデヒド化合物を作
る方法が提案されている。これはアリールヨーダイド、
ベンジルハライド、ビニールヨーダイド、アリルハライ
ドなどを一酸化炭素と水素化スズとパラジュウム触媒を
使って反応させハロゲン原子をアルデヒド基（ＣＨＯ）
に変換するものである。ここにおいてハロゲン原子の代
わりにトリフルオロメチルスルフィニルオキシ基を置換
したトリフラート化合物例えば、４−ｔ−ブチル−１−
シクロヘキセニルトリフレートを同様にしてホルミル化
した例が明らかにされている（Ｊ．Ａｍ．Ｃｈｅｍ，Ｓ
ｏｃ．，１９８６，１０８，４５２−４６１）。しかし
ながら、目的物を収率よく取得するためには加圧を必要
とし、改善されなければならない。There has been proposed a method for producing an aldehyde compound by using carbon monoxide and tin hydride in the presence of an organic halogenated compound as a catalyst. This is an aryl iodide,
Benzyl halide, vinyl iodide, allyl halide, etc. are reacted with carbon monoxide, tin hydride and palladium catalyst to convert halogen atom to aldehyde group (CHO).
Is converted to Here, a triflate compound in which a trifluoromethylsulfinyloxy group is substituted instead of a halogen atom, for example, 4-t-butyl-1-
A similar formylation of cyclohexenyl triflate has been revealed (J. Am. Chem, S.
oc. , 1986, 108, 452-461). However, in order to obtain the target product in good yield, pressurization is required and it must be improved.
【０００４】[0004]
【発明が解決しようとする課題】本件発明は、炭素源と
して一酸化炭素を使用し、ケイ素水素化物をプロトン源
として、トリフラート化化合物をアルデヒト化合物に変
換する新規な方法を提供するものである。DISCLOSURE OF THE INVENTION The present invention provides a novel method for converting a triflated compound into an aldecht compound using carbon monoxide as a carbon source and silicon hydride as a proton source.
【０００５】[0005]
【課題を解決するための手段】トリフラート化化合物を
触媒と共に溶媒に懸濁し、加温して一酸化炭素を導入す
る。次いでケイ素水素化物を加え反応させる。ここにお
いてトリフラート化化合物とはアリールトリフラート又
はエノールトリフラート或いは脂肪族炭化水素トリフラ
ートのいずれでもよく種類を問わない。具体的に代表的
なものを例示すれば、フェニールトリフラート、ナフチ
ルトリフラート、キノリルトリフラート、シクロヘキセ
ントリフラート、シクロオクテントリフラート、シクロ
ペンテントリフラート、ブタントリフラート、ヘキサン
トリフラート、ペンタントリフラート、ヘキサントリフ
ラート、オクタントリフラートなどであり、これらは置
換基を有していないものは言うに及ばず置換基を持って
いても、本件発明の対象とすることができる。Means for Solving the Problems A triflated compound is suspended in a solvent together with a catalyst and heated to introduce carbon monoxide. Then, silicon hydride is added and reacted. Here, the triflated compound may be an aryl triflate, an enol triflate, or an aliphatic hydrocarbon triflate and may be of any kind. Specific examples are phenyl triflate, naphthyl triflate, quinolyl triflate, cyclohexene triflate, cyclooctene triflate, cyclopentene triflate, butane triflate, hexane triflate, pentane triflate, hexane triflate, octane triflate, and the like. These can be the subject of the present invention even if they have a substituent as well as those not having a substituent.
【０００６】次に、触媒として使用されるものは、パラ
ジウムアセテート、ニッケルアセテート等と配位子たる
１，３−ビスジフェニルホスフィノプロパン、１，１’
−ビスジフェニルホスフィノフェロセン等との錯化合物
を使用する。かかる錯化合物は反応系内で生成させるこ
とができるので、予め準備することを排除するものでは
ないが、特に準備することを必要とはしない。Next, those used as catalysts are palladium acetate, nickel acetate, etc. and 1,3-bisdiphenylphosphinopropane and 1,1 'which are ligands.
-A complex compound with bisdiphenylphosphinoferrocene or the like is used. Since such a complex compound can be formed in the reaction system, preparation in advance is not excluded, but preparation in particular is not necessary.
【０００７】使用される溶媒は反応に関与しないもので
あればよく、特に制限がある訳ではないが、好適には
Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシ
ド、トリエチルアミン、ピリジン、ジメチルアニリン、
エチルエーテル、イソプロピルエーテル等が挙げられ
る。反応は、室温及至加熱下で進行せしめられるもので
あるが、熱を加えたほうが反応の進行を促進するもので
あることは一般の化学反応と同様である。The solvent used is not particularly limited as long as it does not participate in the reaction, but preferably N, N-dimethylformamide, dimethylsulfoxide, triethylamine, pyridine, dimethylaniline,
Examples thereof include ethyl ether and isopropyl ether. The reaction is allowed to proceed at room temperature and under heating, but it is similar to a general chemical reaction that the application of heat accelerates the reaction.
【０００８】一酸化炭素は常圧で導入されるところ、そ
の導入によって、反応系に顕著な色相の変化が現れるの
で、その変化が現れた時点で一酸化炭素の必要量は満た
されているから、導入を止める。When carbon monoxide is introduced at atmospheric pressure, the introduction of the carbon monoxide causes a marked change in the hue of the reaction system. At that time, the necessary amount of carbon monoxide is satisfied. , Stop the introduction.
【０００９】次に、プロトン源としてのケイ素水素化物
としては、トリアルキルシラン例えばトリエチルシラ
ン、トリブチルシラン、トリヘキシルシラン、トリオク
チルシラン等のほかジメチルフェニルシラン等も挙げら
れる。これらは前記した溶媒に溶かして反応に供するの
が好都合である。Examples of the silicon hydride as a proton source include trialkylsilanes such as triethylsilane, tributylsilane, trihexylsilane, trioctylsilane and dimethylphenylsilane. Conveniently, these are dissolved in the above-mentioned solvent and used for the reaction.
【００１０】かくて系内に生成しているアルデヒド化化
合物は一般に行われているところに従いエーテル、エス
テル、ヘキサン、ベンゼン、トルエン等で抽出され取得
される。The aldehyde compound thus produced in the system is obtained by extraction with ether, ester, hexane, benzene, toluene, etc. in a conventional manner.
【００１１】[0011]
【実施例】以下具体例を記述して本件発明方法を詳しく
説明するが、これによって本件発明が左右されるもので
はない。 実施例１ ４−ｔ−ブチルフェニルトリフルオロスルホネート１ｍ
ｍｏｌ、酢酸パラジウム（ＩＩ）０．０２ｍｍｏｌ、
１，３−ビス（ジフェニルホスフィノ）プロパン０．０
２ｍｍｏｌ、ジメチルホルムアミド５ｍｌの混合物を撹
拌下、７０℃に過熱した後、一酸化炭素を２０分間にわ
たって吹き込んだ。この時点で、溶液の色が淡褐色から
濃褐色に顕著に変化した。そこでトリオクチルシラン
２．０ｍｍｏｌとトリエチルアミン２．５ｍｍｏｌとを
マイクロシリンジを用いて滴下した。その後同温度で、
原料化合物のＴＬＣ検出が無くなるまで撹拌を続けた。
反応液に水を加えて、エーテル抽出をし、抽出物を集め
て水洗し、飽和重曹水、飽和食塩水の順に洗浄して硫酸
ナトリウムで乾燥し、濃縮した。粗生成物をカラムクロ
マトグラフイーで精製し、４−ｔ−ブチルベンツアルテ
ヒドを得た。反応収率８９％The method of the present invention will be described in detail below with reference to specific examples, but the present invention is not influenced thereby. Example 1 4-t-butylphenyl trifluorosulfonate 1 m
mol, palladium (II) acetate 0.02 mmol,
1,3-bis (diphenylphosphino) propane 0.0
A mixture of 2 mmol and 5 ml of dimethylformamide was heated to 70 ° C. with stirring, and then carbon monoxide was bubbled in for 20 minutes. At this point, the color of the solution changed significantly from light brown to dark brown. Therefore, 2.0 mmol of trioctylsilane and 2.5 mmol of triethylamine were added dropwise using a microsyringe. Then at the same temperature,
Stirring was continued until there was no TLC detection of the starting compound.
Water was added to the reaction solution, and the mixture was extracted with ether. The extracts were collected, washed with water, washed with saturated aqueous sodium hydrogen carbonate and saturated brine in that order, dried over sodium sulfate, and concentrated. The crude product was purified by column chromatography to give 4-t-butylbenzartehde. Reaction yield 89%
【００１２】実施例２ ２−ナフチルトリフレート１ｍｍｏｌ酢酸パラジウム
（ＩＩ）０．０３ｍｍｏｌ、１，３−ビス（ジフェニル
ホスフィノ）プロパン０．０２ｍｍｏｌ、ジメチルホル
ムアミド５ｍｌの混合物を撹拌下、７０℃に過熱した
後、一酸化炭素を２０分間にわたって吹き込んだ。この
時点で、溶液の色が淡褐色から濃褐色に顕著に変化し
た。そこでトリオクチルシラン２．０ｍｍｏｌとトリエ
チルアミン２．５ｍｍｏｌとをマイクロシリンジを用い
て滴下した。その後同温度で、３．５時間撹拌を続け
た。反応液に水を加えて、エーテル抽出をし、抽出物を
集めて水洗し、飽和重曹水、飽和食塩水の順に洗浄して
硫酸ナトリウムで乾燥し、濃縮した。粗生成物をカラム
クロマトグラフイーで精製し、２−ナフチルアルテヒド
を得た。収率９４％Example 2 2-Naphthyl triflate 1 mmol Palladium (II) acetate 0.03 mmol, 1,3-bis (diphenylphosphino) propane 0.02 mmol, 5 ml of dimethylformamide were stirred and heated to 70 ° C. After that, carbon monoxide was bubbled in for 20 minutes. At this point, the color of the solution changed significantly from light brown to dark brown. Therefore, 2.0 mmol of trioctylsilane and 2.5 mmol of triethylamine were added dropwise using a microsyringe. Then, stirring was continued at the same temperature for 3.5 hours. Water was added to the reaction solution, and the mixture was extracted with ether. The extracts were collected, washed with water, washed with saturated aqueous sodium hydrogen carbonate and saturated brine in that order, dried over sodium sulfate, and concentrated. The crude product was purified by column chromatography to give 2-naphthyl aldehyde. 94% yield
【００１３】実施例３ 実施例２において１，３−ビス（ジフェニルホスフィ
ノ）プロパンを１，１−ビス（ジフェニルホスフィノ）
フェロセンに換え、トリオクチルシランとトリエチルア
ミンを２５分かけて加え、すぐに反応を止めた他は実施
例２と同様にして２−ナフチルアルデヒドを得た。収率
８９％Example 3 In Example 2, 1,3-bis (diphenylphosphino) propane was replaced with 1,1-bis (diphenylphosphino).
In place of ferrocene, trioctylsilane and triethylamine were added over 25 minutes, and the reaction was stopped immediately, to obtain 2-naphthylaldehyde in the same manner as in Example 2. Yield 89%
【００１４】実施例４〜１０ 実施例１において使用した原料化合物４−ｔ−ブチルフ
ェニルトリフルオロスルホネートを表１に示す化合物に
代えたほかは実施例１と同様にして夫々対応するアルテ
ヒド化合物を得た。原料名、生成物名、収率等を表１に
示す。Examples 4 to 10 In the same manner as in Example 1 except that the raw material compound 4-t-butylphenyltrifluorosulfonate used in Example 1 was replaced by the compounds shown in Table 1, the corresponding artehydride compounds were obtained. It was The raw material name, product name, yield, etc. are shown in Table 1.
【表１】 [Table 1]
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成８年６月２６日[Submission date] June 26, 1996
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の名称[Correction target item name] Name of invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【発明の名称】 アルデヒド化方法Title of the invention Aldehylation method
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 47/544 9049−4Ｈ Ｃ０７Ｃ 47/544 47/546 9049−4Ｈ 47/546 47/575 9049−4Ｈ 47/575 67/313 67/313 69/757 69/757 Ｃ 69/76 69/76 Ｚ Ｃ０７Ｄ 239/26 Ｃ０７Ｄ 239/26 317/60 317/60 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication location C07C 47/544 9049-4H C07C 47/544 47/546 9049-4H 47/546 47/575 9049- 4H 47/575 67/313 67/313 69/757 69/757 C 69/76 69/76 Z C07D 239/26 C07D 239/26 317/60 317/60 // C07B 61/00 300 C07B 61/00 300
Claims (2)
素を炭素源とし、プロトン源としてケイ素水素化物を使
用し、触媒の存在下、反応させることを特徴とするトリ
フラート化部分をアルデヒドに変える方法。1. A method for converting a triflated moiety into an aldehyde, which comprises reacting a triflated compound with carbon monoxide as a carbon source and silicon hydride as a proton source in the presence of a catalyst. .
合物がα、β−不飽和のトリフラート化合物である請求
項１記載の方法2. The method according to claim 1, wherein the triflated compound according to claim 1 is an α, β-unsaturated triflate compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8075107A JPH09227439A (en) | 1996-02-22 | 1996-02-22 | Aldehyde formation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8075107A JPH09227439A (en) | 1996-02-22 | 1996-02-22 | Aldehyde formation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09227439A true JPH09227439A (en) | 1997-09-02 |
Family
ID=13566624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8075107A Pending JPH09227439A (en) | 1996-02-22 | 1996-02-22 | Aldehyde formation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09227439A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010532759A (en) * | 2007-07-06 | 2010-10-14 | パラテック ファーマシューティカルズ インコーポレイテッド | Method for the synthesis of substituted tetracycline compounds |
-
1996
- 1996-02-22 JP JP8075107A patent/JPH09227439A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010532759A (en) * | 2007-07-06 | 2010-10-14 | パラテック ファーマシューティカルズ インコーポレイテッド | Method for the synthesis of substituted tetracycline compounds |
| JP2011020996A (en) * | 2007-07-06 | 2011-02-03 | Paratek Pharmaceuticals Inc | Method for synthesizing substituted tetracycline compound |
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