TWI789467B - 在溶劑作用下進行二異丁烯之鈀催化羥基羰基化的方法 - Google Patents

在溶劑作用下進行二異丁烯之鈀催化羥基羰基化的方法 Download PDF

Info

Publication number
TWI789467B
TWI789467B TW107145635A TW107145635A TWI789467B TW I789467 B TWI789467 B TW I789467B TW 107145635 A TW107145635 A TW 107145635A TW 107145635 A TW107145635 A TW 107145635A TW I789467 B TWI789467 B TW I789467B
Authority
TW
Taiwan
Prior art keywords
diisobutene
reaction
palladium
reaction mixture
item
Prior art date
Application number
TW107145635A
Other languages
English (en)
Other versions
TW201930248A (zh
Inventor
桑睿
彼得 庫米伊克
董開武
雷夫 傑克斯泰爾
馬席爾斯 貝勒
羅柏特 法蘭克
Original Assignee
德商贏創運營有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 德商贏創運營有限公司 filed Critical 德商贏創運營有限公司
Publication of TW201930248A publication Critical patent/TW201930248A/zh
Application granted granted Critical
Publication of TWI789467B publication Critical patent/TWI789467B/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—Halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/50—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/126—Acids containing more than four carbon atoms
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0202—Polynuclearity
    • B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • 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
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • 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
    • B01J2531/842—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/126—Acids containing more than four carbon atoms
    • C07C53/128—Acids containing more than four carbon atoms the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

在溶劑作用下進行二異丁烯之鈀催化羥基羰基化的方法。

Description

在溶劑作用下進行二異丁烯之鈀催化羥基羰基化的方法
本發明係關於在溶劑作用下進行二異丁烯之鈀催化羥基羰基化的方法。
包括丙酸、己二酸以及脂肪酸的羧酸用於製備聚合物、藥物、溶劑和食品添加劑。產生羧酸的途徑通常包括烴類、醇類或醛類的氧化，經由臭氧分解的烯烴的氧化裂解，甘油三酯、腈、酯或醯胺的水解，格氏試劑(Grignard)或有機鋰試劑的羧化，以及鹵化和隨後鹵代反應中的甲基酮的水解。
烯烴的羥基羧化是用於獲得羧酸的非常有前途以及環境友好的方法。經由甲醇的羰基化產生乙酸，其與碘化物進行。在Koch反應中，向烯烴中加入水和一氧化碳是經由強鹼催化的。該方法對於形成二級和三級碳陽離子的烯烴 是有效的，例如，異丁烯至新戊酸。通過同時向烯烴/炔烴中加入CO和H2O而發生的羥基羧化提供合成羧酸直接且方便的方法。
本發明之目的係提供在二異丁烯(DIBN)之鈀催化羥基羰基化中的良好轉換方法。該反應必須在一個步驟中進行。
經由如申請專利範圍第1項所述之方法完成該目的。
方法包含以下步驟：a)加入二異丁烯，b)加入含有鈀的化合物，其中該鈀係具有能形成錯合物之能力，c)加入配位體L1：
Figure 107145635-A0305-02-0004-1
d)加入乙酸，e)進料CO，f)加熱反應混合物以使該二異丁烯轉變為化合物P1：
Figure 107145635-A0305-02-0004-2
在該方法的一個變化形中，在方法步驟b)中的該化合物中係選自於：PdCl2、PdBr2、Pd(acac)2、Pd(dba)2(dba=二苯乙烯基丙酮)、PdCl2(CH3CN)2。
在該方法的一個變化形中，該方法步驟b)中之該化合物係Pd(acac)2。
在該方法的一個變化形中，該方法包含額外的反應步驟g)：g)加入對甲苯磺酸(PTSA)。
在該方法的一個變化形中，在方法步驟f)中該反應混合物係加熱至80℃至160℃的範圍之溫度，較佳係在100℃至140℃的範圍之溫度。
在該方法的一個變化形中，在方法步驟e)中進料該CO以使該反應在20巴至60巴之範圍的CO壓力下進行，較佳係30巴至50巴之範圍。
經由以下的工作實施例更詳細地闡述本發明。
Figure 107145635-A0305-02-0005-3
在4mL小燒瓶中加入[Pd(acac)2](3.05mg,0.25mol%)、L1(20.64mg,1.0mol%)、PTSA*H2O(28.5mg,3.75mol%)和已烘箱乾燥的攪拌棒。然後用隔膜(PTFE塗覆的 苯乙烯-丁二烯橡膠)和酚醛樹脂蓋密封小燒瓶。將小燒瓶抽真空並用氬氣再填充三次。H2O(0.5ml)、乙酸(1.5ml)以及二異丁烯(DIBN)(4.0mmol)經由針筒加入至小燒瓶。將小燒瓶至於合金板上，在氬氣氛下將其轉移至Parr Instruments的4560系列高壓滅菌器(300ml)中。用CO沖洗高壓滅菌器三次後，在室溫下CO的壓力增加到40巴。反應在120℃下進行20小時。在反應結束時，將高壓滅菌器冷卻至室溫並小心地解壓。然後加入異辛烷(100μl)作為內部標準品。經由GC分析測量轉化率。
以改變溶劑重複上述實驗。維持所有其他的參數。
該結果整理如下表中。
Figure 107145635-A0305-02-0006-4
 *本發明方法
如實驗結果所示，該目的通過本發明的方法實現。

Claims (5)

  1. 一種進行二異丁烯之鈀催化羥基羰基化的方法，其包含以下步驟：a)加入二異丁烯，b)加入含有鈀的化合物，其中該鈀係具有能形成錯合物之能力，c)加入配位體L1：
    Figure 107145635-A0305-02-0007-5
     d)加入乙酸，e)進料CO以獲得反應混合物，f)加熱該反應混合物以使該二異丁烯轉變為化合物P1：
    Figure 107145635-A0305-02-0007-6
  2. 如申請專利範圍第1項所述之方法，其中在方法步驟b)中的該化合物係選自於：PdCl2、PdBr2、Pd(acac)2、Pd(dba)2(dba=二苯乙烯基丙酮)、PdCl2(CH3CN)2。
  3. 如申請專利範圍第1項及第2項任一項所述之方法，其中該方法包含額外的反應步驟g)：g)加入對甲苯磺酸。
  4. 如申請專利範圍第1項至第2項中任一項所述之方法，其中在方法步驟f)中，該反應混合物係加熱至80℃至160℃的範圍之溫度。
  5. 如申請專利範圍第1項至第2項中任一項所述之方法，其中在方法步驟e)中進料該CO以使該反應在20巴至60巴之範圍的CO壓力下進行。
TW107145635A 2017-12-21 2018-12-18 在溶劑作用下進行二異丁烯之鈀催化羥基羰基化的方法 TWI789467B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
??17209307.2 2017-12-21
EP17209307.2A EP3502082B1 (de) 2017-12-21 2017-12-21 Verfahren zur pd-katalysierten hydroxycarbonylierung von diisobuten: einfluss des lösungsmittels
EP17209307.2 2017-12-21

Publications (2)

Publication Number Publication Date
TW201930248A TW201930248A (zh) 2019-08-01
TWI789467B true TWI789467B (zh) 2023-01-11

Family

ID=60811834

Family Applications (1)

Application Number Title Priority Date Filing Date
TW107145635A TWI789467B (zh) 2017-12-21 2018-12-18 在溶劑作用下進行二異丁烯之鈀催化羥基羰基化的方法

Country Status (12)

Country Link
US (1) US10494324B2 (zh)
EP (1) EP3502082B1 (zh)
JP (1) JP6665272B2 (zh)
KR (1) KR102144335B1 (zh)
CN (1) CN109942402B (zh)
CA (1) CA3028181C (zh)
ES (1) ES2777632T3 (zh)
MX (1) MX2018015528A (zh)
MY (1) MY191766A (zh)
PL (1) PL3502082T3 (zh)
TW (1) TWI789467B (zh)
ZA (1) ZA201808496B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3502084B1 (de) * 2017-12-21 2020-02-12 Evonik Operations GmbH Verfahren zur direkten umsetzung von diisobuten zu einer carbonsäure

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201402819A (zh) * 2012-07-02 2014-01-16 Oxea Gmbh 異壬基衍生物之製造方法
CN106187735A (zh) * 2016-07-07 2016-12-07 河北华旭化工有限公司 二异丁烯羰基合成特戊酸和2,2,4,4‑四甲基戊酸的方法
TW201716422A (zh) * 2015-07-23 2017-05-16 贏創德固賽有限責任公司 二茂鐵基化合物及以其為基礎之用於乙烯系不飽和化合物之烷氧羰基化的鈀觸媒

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE887644C (de) * 1943-07-21 1953-08-24 Chemische Verwertungsgesellsch Verfahren zur Herstellung von Carbonsaeuren
US2470859A (en) * 1948-02-25 1949-05-24 Du Pont Nonanoic acid
US3641074A (en) * 1969-02-25 1972-02-08 Union Oil Co Carbonylation of olefins
US3968133A (en) * 1974-11-25 1976-07-06 Texaco Inc. Carboxylation process for preparing linear fatty acids or esters
DE2709438C3 (de) * 1977-03-04 1980-01-17 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von C6. bis C20 Alkylcarbonsäuren
JP3516405B2 (ja) * 1992-04-08 2004-04-05 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ パラジウムホスフィン触媒を用いるカルボニル化法
TW349088B (en) * 1994-12-19 1999-01-01 Eastman Chem Co Carbonylation of olefins
ZA965990B (en) 1995-07-17 1997-02-24 Shell Int Research Process for the continuous carbonylation of olefins.
EP3502084B1 (de) * 2017-12-21 2020-02-12 Evonik Operations GmbH Verfahren zur direkten umsetzung von diisobuten zu einer carbonsäure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201402819A (zh) * 2012-07-02 2014-01-16 Oxea Gmbh 異壬基衍生物之製造方法
TW201716422A (zh) * 2015-07-23 2017-05-16 贏創德固賽有限責任公司 二茂鐵基化合物及以其為基礎之用於乙烯系不飽和化合物之烷氧羰基化的鈀觸媒
CN106187735A (zh) * 2016-07-07 2016-12-07 河北华旭化工有限公司 二异丁烯羰基合成特戊酸和2,2,4,4‑四甲基戊酸的方法

Also Published As

Publication number Publication date
ES2777632T3 (es) 2020-08-05
JP2019112399A (ja) 2019-07-11
TW201930248A (zh) 2019-08-01
MY191766A (en) 2022-07-14
US20190194111A1 (en) 2019-06-27
CN109942402B (zh) 2022-06-03
PL3502082T3 (pl) 2020-07-27
KR102144335B1 (ko) 2020-08-13
EP3502082B1 (de) 2020-02-12
MX2018015528A (es) 2019-06-24
CN109942402A (zh) 2019-06-28
JP6665272B2 (ja) 2020-03-13
CA3028181A1 (en) 2019-06-21
ZA201808496B (en) 2019-09-25
EP3502082A1 (de) 2019-06-26
CA3028181C (en) 2021-02-09
KR20190075842A (ko) 2019-07-01
US10494324B2 (en) 2019-12-03

Similar Documents

Publication Publication Date Title
TWI789468B (zh) Ｏ之比率來進行二異丁烯之鈀催化羥基羰基化的方法
TWI790332B (zh) 在乙酸／二異丁烯比率下進行二異丁烯之鈀催化羥基羰基化的方法
TWI789467B (zh) 在溶劑作用下進行二異丁烯之鈀催化羥基羰基化的方法
TWI798315B (zh) 以配位體／鈀之比率進行二異丁烯之鈀催化羥基羰基化的方法
TWI779141B (zh) 在硫酸/配位體比率下進行二異丁烯之鈀催化羥基羰基化的方法
JP6715314B2 (ja) アルケンをカルボン酸に直接転換する方法