JPS6121730A - Catalyst for producing cinnamic acid esters - Google Patents
Catalyst for producing cinnamic acid estersInfo
- Publication number
- JPS6121730A JPS6121730A JP59142891A JP14289184A JPS6121730A JP S6121730 A JPS6121730 A JP S6121730A JP 59142891 A JP59142891 A JP 59142891A JP 14289184 A JP14289184 A JP 14289184A JP S6121730 A JPS6121730 A JP S6121730A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- palladium
- salt
- cinnamic acid
- acid esters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- 150000001851 cinnamic acid derivatives Chemical class 0.000 title claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 150000004820 halides Chemical class 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 150000003440 styrenes Chemical class 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 159000000014 iron salts Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 150000001879 copper Chemical class 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 4
- 150000002505 iron Chemical class 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract 1
- -1 platinum group metals Chemical class 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- WYOIGGSUICKDNZ-UHFFFAOYSA-N 2,3,5,6,7,8-hexahydropyrrolizin-1-one Chemical compound C1CCC2C(=O)CCN21 WYOIGGSUICKDNZ-UHFFFAOYSA-N 0.000 description 1
- HMKKIXGYKWDQSV-SDNWHVSQSA-N 2-Pentyl-3-phenyl-2-propenal Chemical compound CCCCC\C(C=O)=C/C1=CC=CC=C1 HMKKIXGYKWDQSV-SDNWHVSQSA-N 0.000 description 1
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 241000723347 Cinnamomum Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000003684 Perkin reaction Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- 235000017803 cinnamon Nutrition 0.000 description 1
- 229940019836 cyclamen aldehyde Drugs 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- PNLSTDKQAPNMDU-UHFFFAOYSA-N hept-1-enylbenzene Chemical compound CCCCCC=CC1=CC=CC=C1 PNLSTDKQAPNMDU-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000002092 orthoester group Chemical group 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 description 1
- DBTMQFKUVICLQN-UHFFFAOYSA-K scandium(3+);triacetate Chemical compound [Sc+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBTMQFKUVICLQN-UHFFFAOYSA-K 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 1
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
発明の目的
（イ）産業上の利用分野
本発明はアルコールの存在下にスチレン類を酸化的にカ
ルボニル化して桂皮酸エステル類を製造する際に使用す
る触媒に関するものである。[Detailed description of the invention] Purpose of the invention (a) Industrial application field The present invention relates to a catalyst used in the production of cinnamic acid esters by oxidative carbonylation of styrenes in the presence of alcohol. be.
（ロ）従来の技術
桂皮酸は桂皮アルデヒド、シクラメンアルデヒド、β−
アミル桂皮アルデヒドなどとともに香料原料として使用
されるばかりでなく農薬原料としても使用されており、
実験室的規模ではＰｅｒｋｉｎ反応により製造すること
ができる。(b) Conventional technology Cinnamic acid is cinnamaldehyde, cyclamenaldehyde, β-
Along with amyl cinnamaldehyde, it is used not only as a raw material for fragrances, but also as a raw material for agricultural chemicals.
On a laboratory scale, it can be produced by the Perkin reaction.
従来、スチレンの酸化的カルボニル化反応により桂皮酸
エステルを製造する方法としては、（イ）白金族金属又
はその化合物（ロ）銅塩又は鉄塩およびｆ）アルカリ金
属、アルカリ土類金属、アルミニウム族金属から選ばれ
る金属の有機酸塩とから構成される触媒を使用する例が
知られている（％開昭！ｔ−／！１２４−号公報）。Conventionally, methods for producing cinnamic acid esters by oxidative carbonylation reaction of styrene include (a) platinum group metals or their compounds, (b) copper salts or iron salts, and f) alkali metals, alkaline earth metals, and aluminum group metals. An example of using a catalyst composed of an organic acid salt of a metal selected from metals is known (%Kaisho!t-/!124-publication).
また、エチレングリコールエーテル系溶媒中、（イ）白
金族金属またはその塩類、←）銅または鉄の塩類および
（ハ）アルカリ金属またはアルカリ土類金属の水酸化物
、炭酸塩、酢酸塩から選ばれる７種以上の化合物よりな
る触媒系を使用する例が知られている（特開昭６７−７
０１３６号公報）。Also, in an ethylene glycol ether solvent, selected from (a) platinum group metals or their salts, ←) copper or iron salts, and (c) alkali metal or alkaline earth metal hydroxides, carbonates, and acetates. An example of using a catalyst system consisting of seven or more kinds of compounds is known (Japanese Patent Application Laid-open No. 67-7
Publication No. 0136).
本発明は、高活性で、しかも長寿命で桂皮酸エステルを
製造することができる触媒の提供を目的とする。An object of the present invention is to provide a catalyst that can produce cinnamic acid esters with high activity and long life.
発明の構成
本発明は、
スチレン類と、炭素原子数／〜≠の脂肪族アルコール、
一酸化炭素および酸素とを反応させて桂皮酸エステル類
を製造する触媒であって、（ａ）パラジウム金属または
その化合物、（’ｂ）銅塩または鉄塩および（ｃ）周期
表ＩＩＩａ族に属する元素の塩を含有し、かつ、（ａ）
、（ｂ）および（ｃ）のいずれか一つがハロゲン化物で
あることを特徴とする触媒
を、要旨とする。Structure of the Invention The present invention comprises styrenes, an aliphatic alcohol having a number of carbon atoms/~≠,
A catalyst for producing cinnamic acid esters by reacting carbon monoxide and oxygen, comprising (a) palladium metal or its compound, ('b) copper salt or iron salt, and (c) belonging to Group IIIa of the periodic table. containing a salt of the element, and (a)
, (b) and (c) is a halide.
本発明方法において使用されるスチレン類としては、一
般式
（式中、Ｒ１は水素、ハロゲン、炭素原子数ｌ〜グのア
ルキル基または炭素原子数ｌ−≠のアルコキシ基を表わ
し、Ｒ１は水素または炭素原子数／、７のアルキル基を
表わす。）
で示されるスチレン類を挙げることができ、具体的には
、スチレン、β−メチル・スチレン、ｐ−メｆルスチレ
ン、ｐ−メトキ７ステレン、ｐ−クロルスチレン、β−
メチル−ｐ−イングロビルスチレン、β−アミルスチレ
ン等が挙げられる。The styrenes used in the method of the present invention have the general formula (wherein R1 represents hydrogen, halogen, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1-≠ carbon atoms, and R1 represents hydrogen or Represents an alkyl group having a carbon atom number/, 7. -Chlorstyrene, β-
Examples include methyl-p-inglobylstyrene and β-amylstyrene.
炭素原子数／〜≠の脂肪族アルコールの具体例としては
、メタノール、エタノール、イングロビルアルコール、
ｎ−ブチルアルコール、を−７’チルアルコール等が挙
げられるが、アセタール、ケタール、カルボン酸のオル
トエステル、ジアルコキシシクロアルカン、オルトホウ
酸エステル等の反応系内で解離して上記のアルコールを
放出し得る化合物を用いることもできる。Specific examples of aliphatic alcohols having carbon atoms/~≠ include methanol, ethanol, inglobil alcohol,
Examples include n-butyl alcohol and -7'-ethyl alcohol; however, acetals, ketals, carboxylic acid orthoesters, dialkoxycycloalkanes, orthoboric acid esters, etc. are dissociated in the reaction system to release the above alcohols. It is also possible to use the compounds obtained.
これらのアルコールを使用することにより対応スるアル
コールエステル（桂皮ｆｆアルコールエステル）を生成
する。また、基質の一つである一酸化炭素および酸素は
純粋な状態で使用することもできるが、窒素、アルゴン
等の不活性なガスで稀釈して使用することも出来る。By using these alcohols, the corresponding alcohol esters (cinnamon ff alcohol esters) are produced. Further, carbon monoxide and oxygen, which are one of the substrates, can be used in a pure state, but they can also be used after being diluted with an inert gas such as nitrogen or argon.
本発明の触媒は（ａ）パラジウム金属またはその化合物
、（ｂ）銅または鉄の塩および（０）周期表１ｅａ族に
属する元素の塩とから成り、かつ、（ａ）、（ｂ）ある
いは（ｃ）のいずれか一つはハロゲン化物である。The catalyst of the present invention comprises (a) palladium metal or a compound thereof, (b) a salt of copper or iron, and (0) a salt of an element belonging to group 1ea of the periodic table, and (a), (b) or ( Any one of c) is a halide.
パラジウムとしては、パラジウム黒、担体付き金属パラ
ジウム等の金属パラジウム、テトラキス（トリフェニル
ホスフィン）パラジウム等の０価のパラジウム錯体、塩
化パラジウム、硝酸パラジウム等のλ価のパラジウムの
無機塩、酢酸パラジウム、安息香酸パラジウム等のλ価
のパラジウムのカルボン酸塩、ビス（アセチルアセトナ
ート）パラジウム、ビス（トリフェニルホスフィン）ジ
クロロパラジウム等のλ価のパラジウム錯体が挙げられ
る。これらのパラジウムを担体に担持して用いる場合に
は、シリカ、アルミナ、シリカアルミナ、マグネシア、
チタニア、珪藻土、活性炭、グラファイト、炭酸バリウ
ム、炭酸カルシウム等が担体として使用される。Examples of palladium include palladium black, metallic palladium such as supported metallic palladium, zero-valent palladium complexes such as tetrakis(triphenylphosphine)palladium, inorganic salts of λ-valent palladium such as palladium chloride and palladium nitrate, palladium acetate, and benzoic acid. Examples include carboxylates of λ-valent palladium such as acid palladium, and λ-valent palladium complexes such as bis(acetylacetonato)palladium and bis(triphenylphosphine)dichloropalladium. When using palladium supported on a carrier, silica, alumina, silica alumina, magnesia,
Titania, diatomaceous earth, activated carbon, graphite, barium carbonate, calcium carbonate, etc. are used as carriers.
銅または鉄の塩は°有機酸塩でも無機酸塩でもよい。有
機酸の中では脂肪族カルボン酸が特に有効であり、また
無機酸の中ではハロゲン化物が好適に使用される。The copper or iron salts may be organic or inorganic salts. Among organic acids, aliphatic carboxylic acids are particularly effective, and among inorganic acids, halides are preferably used.
皮酸塩等が挙げられるが、特に酢酸塩が有効である。ま
た、銅または鉄のハロゲン化物としては、例えば塩化第
二銅および塩化第二鉄等があげられる。Examples include salts of salts, but acetates are particularly effective. Examples of copper or iron halides include cupric chloride and ferric chloride.
周期表１１［ａ族に属する元素の塩の具体例としては、
塩化スカンジウム、酢酸スカンジウム、塩化イツトリウ
ム、酢酸イツトリウム、硫酸イツトリウム、塩化ランタ
ン、弗化ランタン、臭化ランタン、酢酸ランタン、塩化
第二セリウム、酢酸第二セリウム、塩化プラセオジウム
、酢酸プラセオジウム、塩化混合希土、酢酸混合希土等
である。Periodic Table 11 [Specific examples of salts of elements belonging to group a include:
scandium chloride, scandium acetate, yttrium chloride, yttrium acetate, yttrium sulfate, lanthanum chloride, lanthanum fluoride, lanthanum bromide, lanthanum acetate, ceric chloride, ceric acetate, praseodymium chloride, praseodymium acetate, mixed rare earth chlorides, These include rare earth mixed with acetic acid.
これら触媒として使用する四成分の仕込み混合比率とし
ては、パラジウム金属またはその化合物と銅または鉄の
塩との原子比（ａｔｏｍｉｃｒａｔｉｏ ）は／対／
〜、ｔ ０００より好ましくは／対１ｏ−ｊｏｏの範囲
になるように使用するのが適当であ′る。As for the mixing ratio of these four components used as catalysts, the atomic ratio of palladium metal or its compound to copper or iron salt is /to/
It is appropriate to use a range of 10-joo to t000, preferably 1o-joo.
銅または鉄の塩と周期表ｌ１ｌｌａ族に属する元素の塩
とのモル比は、／対０．０ ／〜／σＯより好ましくは
ｌ対０．／〜１０の範囲になるように使用するのが適当
である。The molar ratio of a salt of copper or iron to a salt of an element belonging to group 11lla of the periodic table is preferably l to 0.0 / to /σO. It is appropriate to use it so that it is in the range of / to 10.
反応溶媒は特に使用しなくても支障はないが場合により
操作を円滑に行なうために適当な不活性溶媒を使用する
ことができる。Although there is no problem even if the reaction solvent is not used, an appropriate inert solvent may be used in some cases to facilitate the operation.
本発明の触媒を使用する桂皮酸エステル類の製造は、反
応温度を高めることにより、桂皮酸エステル類の収率を
向上させることができる。In the production of cinnamic esters using the catalyst of the present invention, the yield of cinnamic esters can be improved by increasing the reaction temperature.
しかし、反応温度をあまシ高くすると二酸化炭素の生成
など副反応の生起により、逆に桂皮酸エステル類の選択
率が低下するので、通常は常温〜２００℃、より好まし
くは４０−／ＡＯ℃の範囲内の反応温度が適当である。However, if the reaction temperature is too high, the selectivity of cinnamic acid esters will decrease due to the occurrence of side reactions such as the production of carbon dioxide. Reaction temperatures within a range are suitable.
本発明方法を実施して得られる反応生成液に用すること
により、桂皮酸エステル類を分離取得することができる
。By using the reaction product liquid obtained by carrying out the method of the present invention, cinnamic acid esters can be separated and obtained.
実施例 次に本発明を実施例によシ更に具体的に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
実施例１
内容積りＯｗｌのスピナー攪拌式ガラス内筒ハステロイ
Ｃ製のオートクレーブに、スチレン７ｍｌ （ｔ ／、
−２ｍｍｏ１）、メタノール３ｍ１（７１１，Ｏｍｍｏ
ｌ ）、０８５％：ｐａ／Ａａ（活性炭にパラジウム′
ｌＣＯ，ｊＭ＊％担持）／、０ｔｒ（θ、Ｏｊ ｍ ｆ
−ａｔｏｍ ）、塩化第二銅０．ＯＡ ７ ｔ （０
１ｍｍｏｌ ）、酢酸ランクｙ ｌ／２水和物０．／６
２９ （００，ｔｍｍｏ：Ｌ）ｉ仕込み、密封後一酸化
炭素１．Ｏｋｇ／ｃｒｌＧｆ圧入した。Example 1 Styrene 7ml (t/,
-2mmo1), methanol 3ml (711, Ommo
), 085%: pa/Aa (palladium' on activated carbon
lCO,jM*% loading)/,0tr(θ,Oj m f
-atom), cupric chloride 0. OA 7t (0
1 mmol), acetic acid rank y l/dihydrate 0. /6
29 (00,tmmo:L) i After preparation and sealing, carbon monoxide 1. Okg/crlGf was press-fitted.
次いでｔ％ＯＸ／馬（酸紫金６容量チ含む窒素ガス）を
圧入し全圧を室温で１０コ、θ〜／ａｄａ とした。Next, t% OX/H (nitrogen gas containing 6 volumes of acid) was injected to bring the total pressure to 10, θ~/ada at room temperature.
オートクレーブを電気炉にて加熱し、１．２０℃に保っ
て３０分間反応を行なった。反応終了後オートクレーブ
を冷却し、放圧した後、反応ガスの組成および生成液の
組成をガスクロマトグラフィーによシ分析した。生成し
た桂皮酸メチルは八６３♂ｔ （／ ０．／ ｍｍｏｌ
）であった。The autoclave was heated in an electric furnace, maintained at 1.20°C, and the reaction was carried out for 30 minutes. After the reaction was completed, the autoclave was cooled and the pressure was released, and then the composition of the reaction gas and the composition of the product liquid were analyzed by gas chromatography. The amount of methyl cinnamate produced was 863♂t (/0./mmol
)Met.
実施例２〜．２／
第１表に示した原料および反応条件に、よシ、実施例１
に準じて反応を行ない、第１表に示した桂皮酸メチルエ
ステルの生成率を得た。Example 2~. 2/ According to the raw materials and reaction conditions shown in Table 1, Example 1
The reaction was carried out according to the method described in Table 1, and the production rates of methyl cinnamic acid ester shown in Table 1 were obtained.
Claims (1)
ール、一酸化炭素および酸素とを反応させて桂皮酸エス
テル類を製造する触媒であって、（ａ）パラジウム金属
またはその化合物、（ｂ）銅塩または鉄塩および（ｃ）
周期表IIIａ族に属する元素の塩を含有し、かつ、（ａ
）、（ｂ）および（ｃ）のいずれか一つがハロゲン化物
であることを特徴とする触媒。(1) A catalyst for producing cinnamic acid esters by reacting styrenes with an aliphatic alcohol having 1 to 4 carbon atoms, carbon monoxide, and oxygen, comprising: (a) palladium metal or its compound; b) copper or iron salts and (c)
contains a salt of an element belonging to group IIIa of the periodic table, and (a
), (b) and (c) is a halide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59142891A JPS6121730A (en) | 1984-07-10 | 1984-07-10 | Catalyst for producing cinnamic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59142891A JPS6121730A (en) | 1984-07-10 | 1984-07-10 | Catalyst for producing cinnamic acid esters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6121730A true JPS6121730A (en) | 1986-01-30 |
| JPH0515503B2 JPH0515503B2 (en) | 1993-03-01 |
Family
ID=15325993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59142891A Granted JPS6121730A (en) | 1984-07-10 | 1984-07-10 | Catalyst for producing cinnamic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6121730A (en) |
-
1984
- 1984-07-10 JP JP59142891A patent/JPS6121730A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0515503B2 (en) | 1993-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kakino et al. | Synthesis of unsymmetrical ketones by palladium-catalyzed cross-coupling reaction of carboxylic anhydrides with organoboron compounds | |
| EP0152075B1 (en) | Process for the production of cinnamic acid esters | |
| JPH0213653B2 (en) | ||
| CN105377804A (en) | Preparation of methyl methacrylate via an oxidative esterification process | |
| JPS6121730A (en) | Catalyst for producing cinnamic acid esters | |
| US3755387A (en) | Vapor phase transvinylation process | |
| CA1120457A (en) | Preparaion of ketones | |
| US3725462A (en) | Process for the manufacture of substituted phenyl esters and optionally substituted phenols | |
| EP0186349B1 (en) | Process for the preparation of cinnamate ester | |
| US4620027A (en) | Catalyst and process for production of cinnamates | |
| JPH0452254B2 (en) | ||
| JPH07100679B2 (en) | Process for producing α- (3-benzoylphenyl) propionic acid or its ester | |
| JPS6323984B2 (en) | ||
| JPH07196573A (en) | Acetophenone production method | |
| JPH0669986B2 (en) | Method for producing cinnamic acid esters | |
| JPS60109545A (en) | Manufacturing method of cinnamic acid esters | |
| JPS60169441A (en) | Manufacturing method of cinnamic acid esters | |
| JP3489324B2 (en) | Method for producing diaryl carbonate | |
| JPS60126245A (en) | Production of cinnamic acid ester | |
| JPH0757738B2 (en) | Method for producing 4-isobutylstyrene | |
| JPS6023661B2 (en) | Manufacturing method of cinnamic acid esters | |
| KR960009677B1 (en) | Preparation of 4-isobutyl styrene | |
| JPH0834762A (en) | Method for producing α-ketone ester | |
| JPS6097935A (en) | Production of cinnamic acid ester | |
| JPS62286953A (en) | Production of cinnamic acid ester |