CN1191497A - 水溶性的钴催化剂、它们的制备方法和它们在包括聚乙二醇作为极性相的两相体系中作为加氢甲酰化催化剂的应用 - Google Patents
水溶性的钴催化剂、它们的制备方法和它们在包括聚乙二醇作为极性相的两相体系中作为加氢甲酰化催化剂的应用 Download PDFInfo
- Publication number
- CN1191497A CN1191497A CN96195733A CN96195733A CN1191497A CN 1191497 A CN1191497 A CN 1191497A CN 96195733 A CN96195733 A CN 96195733A CN 96195733 A CN96195733 A CN 96195733A CN 1191497 A CN1191497 A CN 1191497A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- phase
- preparation
- hydroformylation
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 6
- 239000010941 cobalt Substances 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 3
- 239000002202 Polyethylene glycol Substances 0.000 title 1
- 229920001223 polyethylene glycol Polymers 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 description 13
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 235000013495 cobalt Nutrition 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N caproic aldehyde Natural products CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002512 chemotherapy Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明涉及式(Ⅰ)的羰基钴催化剂,其中,R是－CH(CH2OCH2CH2)2或－C2H4(OCH2CH2)nOY,n=1—12,Y=H或CH3,也涉及它们的制备方法和它们作为加氢甲酰化催化剂的应用。
Description
本发明涉及水溶性钴催化剂、它们的制备方法和它们在包括聚乙二醇作为极性相的一种两相体系中作为加氢甲酰化催化剂的应用。
水溶性催化剂具有很大的工业优越性，这是由于催化剂易于分离且同时作为均相反应的结果，催化剂的选择性高。由于催化剂易于分离所致的能耗显著下降和同时由于选择性高所致的不希望有的副产物量的下降，导致了对开发两相催化剂的兴趣增加。
因此存在提供这类其它化合物的需要。
这一目的可通过式(I)的羰基钴催化剂来达到：
其中R是-CH(CH2OCH2CH2)2或-C2H4(OCH2CH2)nOY，其中n＝1-12，Y＝H或CH3。
本发明化合物是通过将式(II)化合物与醇ROH反应制备的，
此处，X是OH或氯，R如上定义。
式(II)化合物是按D.Seyferth，有机金属化学杂志，1979，178，227-247中的方法制备的。
式(I)化合物在烃烃的加氢甲酰化中具有高转化率和高化学选择性。具有特别意义的是，式CH3(CH2)mCH＝CH2(m＝2-9)的烯烃在包括聚乙二醇作为极性相的一种两相体系中的反应。现已发现，在50-150℃、50-100KPa和催化剂：反应物的浓度比为1∶20-1∶1000的条件下操作是适用的。实施例1
将0.574g(1mmo1)三钴九羰基甲撑三氯甲硅烷(Tricobalt-nonacarbonylmethylindintrichlorsilan)吸收在10ml聚乙烯400中，并在CO气氛中，在80℃加热24小时。随后滤出沉滤。CO含量是13.75g/1(由原子吸收光谱测定)。该化合物是以在聚乙二醇400中的溶液形式存在、并具有强紫色。它与水是完全共溶的，与非极性溶剂(己烷、戊烷等)实际上不互溶。
该溶液的IR谱显示了在羰基区域中的下列谱带：
1887cm-1、1979cm-1、1995cm-1、2029cm-1、2060cm-1。实施例2
将0.574g(1mmo1)三钴九羰基甲撑三氯甲硅烷吸收在10ml1，3-二乙氧基-2-丙醇中，并在CO气氛中、于60℃加热24小时。然后在高真空中蒸馏掉过剩的醇。得到的化合物是以紫色高粘性溶液形式存在。该化合物的液体石蜡中的IR谱显示了在羰基区域中的下列谱带：2037cm-1、2056cm-1。
1H-NMR谱显示了三组信号，各位于：1.03ppm(CH3，d，6H)；3.26ppm(CH2，q，4H)；3.42ppm(CH2，m，4H)；4.01ppm(CH，m，1H)(在d6-苯中测得)。29Si-NMR谱在-53.8ppm(在d8-THF中测得)处显示了单信号。实施例3-6
在1项下制得的化合物在聚乙二醇400中进行的1-己烯加氢甲酰化反应中的应用：
在100ml实验室高压釜中进行催化试验。在一个典型的反应中，2ml已按下述方法制得的聚乙二醇溶液被加入并与2ml1-己烯(16mmol)混合，所说方法是：按(I)所述的方式使三钴九羰基甲撑三氯甲硅烷与聚乙二醇400反应。然后该高压釜充加以70KPa的CO与H21/1的混合物。在搅拌下在120℃加热反应混合物18小时。反应后，加入4ml戊烷以有助于相分离，且作相分离。上部的非极性相含戊烷和反应产物，它们通过与可靠样对比来作气相色谱法鉴定或通过GC-MS鉴定。庚烷用作内标。下部的聚乙二醇相含催化剂可不经预处理而重复使用。结果列于表1。实施例7-13
使用Co3(CO)9CSiX3(X＝OH)(III)的催化试验作为对比实验来进行。其中使用了类似于实施例5-8的方法，其条件列于表1中。
表1
| 实施例a | 温度℃ | 压力KPab | mg Coc | 产率％d | 时间小时 | 选择性正/异e |
| 3456h789101112f13gCO2(CO)8 | 120120120120120120120120120120120120 | 7070707070701264270707070 | 13.7520.6343410.97.87.87.87.811.610.222 | 96.599.599.972.996.898.097.025.098.598.999.895.6i | 181818182424127272242418 | 0.730.750.750.671.40.793.751.811.933.22.960.58 |
a)实施例3-6不用溶剂，实施例7-13使用甲苯作溶剂；b)初始压力；c)反应物：2ml 1-己烯；d)产率是基于消耗的1-己烯量计算的。检测到的主产物是1-庚醛、2-甲基己醛和2-乙基戊醛。在给定的反应条件下，1-己烯的加氢和醛的加氢以得到醇的反应观测不到。e)正/异：1-庚醛/2-甲基己醛+2-乙基戊醛。f)添加三苯基膦(与催化剂的摩尔比1∶1)。g)添加二(二苯基膦基)甲烷(与催化剂的摩尔比1∶1)。h)相分离后再用的催化剂。i)化学选择性：44％的醛/56％的醇。
Claims (7)
1.式(I)的羰基钴催化剂其中R是-CH(CH2OCH2CH2)2或-C2H4(OCH2CH2)nOY，n＝1-12，Y＝H或CH3。
2.制备式(I)化合物的方法，包括使式(II)化合物与醇ROH反应
CO3(CO)9CSiX3 (II)，其中R如上定义，X是OH、Cl。
3.权利要求1中的催化剂作为加氢甲酰化催化剂的应用。
4.根据权利要求3的应用，其中，加氢甲酰化是在50-150℃下进行的。
5.根据权利要求3或4的应用，其中，加氢甲酰化是在50-100KPa下进行的。
6.根据权利要求3-6中至少一项的应用，其中，催化剂：反应物的比率为1∶20-1∶1000。
7.根据权利要求3-6中至少一项的应用，其中使用的反应物是下式(II)的烯烃
CH3(CH2)mCH＝CH2 (II)其中m＝2-9。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19521936A DE19521936C1 (de) | 1995-06-16 | 1995-06-16 | Cobaltcarbonylkatalysator, Verfahren zu seiner Herstellung und seine Verwendung zur Hydroformylierung |
| DE19521936.8 | 1995-06-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1191497A true CN1191497A (zh) | 1998-08-26 |
Family
ID=7764532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96195733A Pending CN1191497A (zh) | 1995-06-16 | 1996-06-03 | 水溶性的钴催化剂、它们的制备方法和它们在包括聚乙二醇作为极性相的两相体系中作为加氢甲酰化催化剂的应用 |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US5840993A (zh) |
| EP (1) | EP0841987B1 (zh) |
| JP (1) | JPH11507588A (zh) |
| KR (1) | KR19990022966A (zh) |
| CN (1) | CN1191497A (zh) |
| AU (1) | AU6004596A (zh) |
| BR (1) | BR9609427A (zh) |
| DE (2) | DE19521936C1 (zh) |
| MX (1) | MX9710180A (zh) |
| MY (1) | MY132172A (zh) |
| PL (1) | PL324021A1 (zh) |
| TW (1) | TW352343B (zh) |
| WO (1) | WO1997000132A1 (zh) |
| ZA (1) | ZA965014B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432363B (zh) * | 2016-09-13 | 2019-02-26 | 天津师范大学 | 一种水溶性三核钴配合物及其制备方法 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4045493A (en) * | 1975-02-03 | 1977-08-30 | Standard Oil Company (Indiana) | Hydroformylation of olefins |
| US4144191A (en) * | 1977-06-06 | 1979-03-13 | The Dow Chemical Company | Amine-resin supported rhodium-cobalt carbonyl bimetallic clusters as novel hydroformylation catalysts |
-
1995
- 1995-06-16 DE DE19521936A patent/DE19521936C1/de not_active Expired - Fee Related
-
1996
- 1996-06-03 PL PL96324021A patent/PL324021A1/xx unknown
- 1996-06-03 AU AU60045/96A patent/AU6004596A/en not_active Abandoned
- 1996-06-03 US US08/981,261 patent/US5840993A/en not_active Expired - Fee Related
- 1996-06-03 EP EP96917490A patent/EP0841987B1/de not_active Expired - Lifetime
- 1996-06-03 KR KR1019970709436A patent/KR19990022966A/ko not_active Application Discontinuation
- 1996-06-03 WO PCT/EP1996/002394 patent/WO1997000132A1/de not_active Application Discontinuation
- 1996-06-03 DE DE59604127T patent/DE59604127D1/de not_active Expired - Fee Related
- 1996-06-03 BR BR9609427-3A patent/BR9609427A/pt not_active IP Right Cessation
- 1996-06-03 MX MX9710180A patent/MX9710180A/es unknown
- 1996-06-03 JP JP9502570A patent/JPH11507588A/ja active Pending
- 1996-06-03 CN CN96195733A patent/CN1191497A/zh active Pending
- 1996-06-13 ZA ZA965014A patent/ZA965014B/xx unknown
- 1996-06-15 MY MYPI96002434A patent/MY132172A/en unknown
- 1996-06-27 TW TW085107758A patent/TW352343B/zh active
Also Published As
| Publication number | Publication date |
|---|---|
| AU6004596A (en) | 1997-01-15 |
| ZA965014B (en) | 1996-07-29 |
| EP0841987A1 (de) | 1998-05-20 |
| EP0841987B1 (de) | 2000-01-05 |
| DE59604127D1 (de) | 2000-02-10 |
| DE19521936C1 (de) | 1996-09-12 |
| MY132172A (en) | 2007-09-28 |
| US5840993A (en) | 1998-11-24 |
| BR9609427A (pt) | 2002-07-16 |
| TW352343B (en) | 1999-02-11 |
| JPH11507588A (ja) | 1999-07-06 |
| PL324021A1 (en) | 1998-05-11 |
| KR19990022966A (ko) | 1999-03-25 |
| MX9710180A (es) | 1998-04-30 |
| WO1997000132A1 (de) | 1997-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20110201844A1 (en) | Catalyst composition for hydroformylation and method for producing aldehyde using the same | |
| JPS62145038A (ja) | オレフインのヒドロホルミル化法 | |
| US4306087A (en) | Hydroformylation of olefinic compounds | |
| GB1594056A (en) | Hydroformylation using catalysts comprising rhodium and diphosphino ligands | |
| CA2326047A1 (en) | Process for hydrocarbonylations in supercritical carbon dioxide | |
| JP3416956B2 (ja) | ヒドロホルミル化法およびビスホスファイト化合物 | |
| EP1339491B1 (en) | Phosphonite ligands, catalyst compositions and hydroformylation process utilizing same | |
| CN111315483A (zh) | 用于烯烃加氢甲酰化的高异构选择性催化剂 | |
| US20020065434A1 (en) | Valeraldehyde and process for its preparation | |
| BRPI1010643B1 (pt) | processo para hidroformilação de álcool alílico para produzir 4-hidroxibutiraldeído | |
| How et al. | A modular family of phosphine-phosphoramidite ligands and their hydroformylation catalysts: steric tuning impacts upon the coordination geometry of trigonal bipyramidal complexes of type [Rh (H)(CO) 2 (P^ P*)] | |
| Muilwijk et al. | A bulky phosphite-modified rhodium catalyst for the hydroformylation of unsaturated fatty acid esters | |
| EP0033554A2 (en) | A process for the hydroformylation of conjugated dienes | |
| US5684208A (en) | Process for preparing pentenals | |
| Sinou et al. | Rhodium‐Catalyzed Hydrogenation of Alkenes by Rhodium/Tris (fluoroalkoxy) phosphane Complexes in Fluorous Biphasic System | |
| WO1997046507A1 (de) | Verfahren zur hydroformylierung und dafür geeignete katalysatoren, die phosphorverbindungen als liganden enthalten | |
| CN1191497A (zh) | 水溶性的钴催化剂、它们的制备方法和它们在包括聚乙二醇作为极性相的两相体系中作为加氢甲酰化催化剂的应用 | |
| KR102340629B1 (ko) | 하이드로포밀화 반응용 헤테로 리간드 배위결합 촉매 조성물 및 이의 용도 | |
| CN100418974C (zh) | 双螯合配体及其在羰基化方法中的用途 | |
| CN113583046B (zh) | 双齿膦配体及其制备方法、应用 | |
| Wencel et al. | Chiral phosphinoazomethinylate salts as new ‘one-step available’ligands for copper-catalyzed asymmetric conjugate addition | |
| DE19630534C1 (de) | Alkylenglykolgruppen enthaltende tertiäre Phosphane | |
| CN112479842B (zh) | 一种4-叔丁基苯丙醛的制备方法 | |
| CN114656501B (zh) | 2,2′-联吡啶骨架双膦配体及其制备方法、应用 | |
| SU696001A1 (ru) | Способ получени формилциклододекана |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |