CN107935878A - 一种由烯烃、一氧化碳和氨气制备一级酰胺的方法 - Google Patents

一种由烯烃、一氧化碳和氨气制备一级酰胺的方法 Download PDF

Info

Publication number
CN107935878A
CN107935878A CN201711154996.1A CN201711154996A CN107935878A CN 107935878 A CN107935878 A CN 107935878A CN 201711154996 A CN201711154996 A CN 201711154996A CN 107935878 A CN107935878 A CN 107935878A
Authority
CN
China
Prior art keywords
alkene
primary amide
phosphine ligands
ammonia
carbon monoxide
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
Application number
CN201711154996.1A
Other languages
English (en)
Inventor
刘晔
王鹏
刘欢
王栋梁
周清
梁文玉
柳磊
路勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China Normal University
Original Assignee
East China Normal University
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 East China Normal University filed Critical East China Normal University
Priority to CN201711154996.1A priority Critical patent/CN107935878A/zh
Publication of CN107935878A publication Critical patent/CN107935878A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • 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
    • B01J2531/822—Rhodium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种由烯烃、一氧化碳和氨气制备一级酰胺的方法，该方法在由膦配体与铑化合物组成的催化剂作用下，以烯烃、一氧化碳和氨气为原料来制备一级酰胺；所采用的膦配体能够保证铑化合物作为催化剂有效催化烯烃的羰化酰胺化反应，从而高收率生成一级酰胺。所述膦配体中还含有N‑杂原子或/和O‑杂原子或/和S‑杂原子。本发明为一锅法合成方法，合成步骤简单；在所选的膦配体和铑化合物组成的催化剂作用下，原料烯烃、一氧化碳和氨气通过“羰化酰胺化反应”生成一级酰胺的收率高；所使用的催化剂催化性能好，寿命稳定。

Description

一种由烯烃、一氧化碳和氨气制备一级酰胺的方法
技术领域
本发明涉及精细化学品的合成方法，尤其是一种在膦配体与铑化合物组成的催化剂作用下，由烯烃、一氧化碳和氨气通过羰化酰胺化反应制备一级酰胺的方法。
背景技术
一级酰胺是重要的有机化合物，广泛用于医药、食品添加剂和香料等领域(Organometallics.,2003,22,24-26；Organometallics.,2003,22,24-26；Chem.Commun.,2007,301-303；Org.Lett.,2009,11,2643-2646；J.Am.Chem.Soc.,1937,59,2262-2264)。通常，一级酰胺通过酰氯、酸酐或酯(活化的羧酸)和氨气(氨水或液氨)通过胺解反应制得(Tetrahedron Lett.2005,46,6879–6882；Synlett.2014,25,85–88)。另外，氰的水解也可以制备一级酰胺(Tetrahedron Lett.2010,51,1589–1591；J.Am.Chem.Soc.2003,125,11539–11544)。但这些方法所用原料昂贵、危险性较高，且反应过程产生有大量副产物生成。
发明内容
本发明的目的在于提供一种由膦配体与铑化合物组成的催化剂的催化作用下，由烯烃制备一级酰胺的方法。该方法以廉价烯烃为原料，通过烯烃与一氧化碳和氨气反应，在膦配体与铑化合物组成的催化剂作用下，通过羰化酰胺化反应制备一级酰胺。
实现本发明目的的具体技术方案是：
一种由烯烃、一氧化碳和氨气制备一级酰胺的方法，特点是：在聚四氟乙烯内衬的不锈钢高压反应釜中依次加入溶剂、烯烃、铑化合物、膦配体和质子酸，充入CO和NH3混合气体，在2.0～8.0MPa总压力下，反应温度为80～150℃，反应1～24小时后，冷却至室温，泄压，分出有机相，乙醚萃取有机产品，得到烯烃转化率为67～99％和一级酰胺收率为38～95％；其中：
所述膦配体与铑化合物的摩尔比为1～20:1；烯烃与铑化合物的摩尔比为200～2000:1；溶剂与烯烃的体积比为1～20:1；CO与NH3体积比为9:1；
所述溶剂为甲醇、乙醇或异丙醇；
所述膦配体为具有以下结构的化合物：
上述膦配体中既有能与过渡金属铑配位的膦配体基团(-PPh2)，又有含具有弱配位能力的N-杂原子或/和O-杂原子或/和S-杂原子。
本发明以烯烃、一氧化碳和氨气为原料，通过过渡金属催化剂(膦配体和铑化合物混合组成)催化的“羰化酰胺化”反应,一步合成一级酰胺，是100％原子经济性合成一级羰化酰胺的绿色合成方法。该合成方法步骤简单；在所选的过渡金属催化剂作用下，烯烃与一氧化碳和氨气反应生成一级酰胺的收率高；所使用催化剂的催化性能好，寿命稳定。
具体实施方式
下面的实施例将具体描述本发明，但不是对本发明的进一步限制；所有实施例均按上述反应条件和步骤进行操作。
实施例1
L1的合成
在N2保护下，向100mL三口烧瓶中加入45mL无水二氯甲烷，然后加入苯胺(5mmol)和三乙胺(15mmol)。搅拌均匀后，于室温下缓慢滴加氯代二苯基膦(5mmol)的20mL无水二氯甲烷溶液。有大量白色沉淀生成。室温下继续搅拌24h.待TLC表明反应完全后，减压蒸馏除去溶剂和过量的三乙胺，然后加入100mL四氢呋喃并充分搅拌，以使三乙胺的盐酸盐完全析出。抽滤2次，并用四氢呋喃洗涤。合并滤液，减压蒸馏除去四氢呋喃后，加入50mL无水二氯甲烷，溶解粗产物，然后用3cm中性氧化铝层抽滤，并用50mL二氯甲烷洗涤中性氧化铝层。合并滤液，减压蒸馏除去二氯甲烷，然后用二氯甲烷和无水乙醚结晶，真空干燥，得白色晶体即为配体L1(收率：85％)，结构如结构式L1所示。1H NMR(δ,ppm,CDCl3):8.25(d,1H,J＝12.0Hz),7.80-7.77(m,4H),7.56-7.50(m,6H),7.10-7.04(m,4H),6.79(t,1H,J＝8.0Hz).31P NMR(δ,ppm,CDCl3):18.69(s)。
实施例2
L2的合成
L2的合成方法和L1的合成方法相同，起始原料换为苯甲胺(收率：80％)。结构如结构式L2所示。1H NMR(δ,ppm,CDCl3):7.80(s,1H),7.36-7.26(m,10H),7.10-7.07(m,3H),6.76-6.74(m,2H),2.01-1.96(m,2H).31P NMR(δ,ppm,CDCl3):17.21(s)。
实施例3
L3的合成
L3的合成方法和L1的合成方法相同，起始原料换为苯乙胺(收率：91％)。结构如结构式L3所示。1H NMR(δ,ppm,CDCl3):7.68(s,1H),7.59-7.54(6H,m),7.52-7.47(4H,m),7.09-7.08(3H,m),6.37-6.35(2H,m),3.48-3.40(2H,m),2.01-1.96(2H,m).31P NMR(δ,ppm,CDCl3):25.43(s)。
实施例4
L4的合成
L4的合成方法和L1的合成方法相同，起始原料换为2-氨基吡啶(收率：42％)。结构如结构式L5所示。1H NMR(δ,ppm,CDCl3):7.97(d,1H,J＝9.0Hz),7.45-7.43(m,3H),7.34-7.30(m,8H),7.04-7.02(m,2H),6.66-6.64(m,1H).31P NMR(δ,ppm,CDCl3):35.23(s).
实施例5
L5的合成
L5的合成方法和L1的合成方法相同，起始原料换为2-氨基噻唑(收率：89％)。结构如结构式L5所示。1H NMR(δ,ppm,CDCl3):8.97(d,1H,J＝4.0Hz),7.49-7.39(m,4H),7.41-7.39(m,6H),7.11(t,1H,J＝4.0Hz),6.82(d,1H,J＝4.0Hz).31P NMR(δ,ppm,CDCl3):41.14(s).
实施例6
L6的合成
L6的合成方法与L1的合成方法相同，起始原料换为2-氨基噻唑啉(收率：71％)。结构如结构式L6所示。1H NMR(δ,ppm,CDCl3):7.85-7.80(m,4H),7.44-7.39(m,6H),3.74(t,2H,J＝8.0Hz),3.28(t,2H,J＝8.0Hz).31P NMR(δ,ppm,CDCl3):25.26(s).
实施例7-10
L7-L10的合成
L7-L10的合成方法与L1的合成方法相同。起始原料分别为2-氨基噁唑啉、2-氨基噁唑、2-氨基环己酮和吡咯烷酮。
实施例11～20
在有聚四氟乙烯内衬的不锈钢高压反应釜中依次加入10mmol 1-辛烯、0.01mmolRh(acac)(CO)2、0.05mmol膦配体(L1～L10)、0.05mmol HBF4和3mL甲醇，充入CO和NH3体积比为9的合成气至4.0MPa，密封后在120℃反应24小时。反应结束后，冷却至室温，泄压，取上层有机相，用气相色谱进行分析，确定对产品缩醛的收率。表1给出使用不同膦配体L1～L10和Rh(acac)(CO)2组成的催化剂催化的1-辛烯羰化酰胺化反应制备一级酰胺的实验结果。
表1膦配体L1～L10和Rh(acac)(CO)2组成的催化剂对1-辛烯羰化酰胺化反应制备一级酰胺a
a Rh(acac)(CO)2 0.1mol％(0.01mmol)，含氮膦配体0.05mmol，1-辛烯10.0mmol，HBF4 0.05mmol，甲醇3mL，CO/NH3(9:1)4.0MPa，120℃，24小时。
b气相色谱分析。
实施例21-31
表2给出在L1和Rh(acac)(CO)2组成的催化剂，对不同α-烯烃的“羰化酰胺化”串联反应催化反应结果。在有聚四氟乙烯内衬的不锈钢高压反应釜中依次加入10mmolα-烯烃、0.01mmol Rh(acac)(CO)2、0.05mmol含氮膦配体L1、0.05mmol HBF4、3mL甲醇，充入CO和NH3体积比为9的合成气至4.0MPa，密封后在120℃反应24小时。反应结束后，冷却至室温，泄压，取反应液，用气相色谱进行分析，确定对产品一级酰胺的收率。
表2膦配体L1和Rh(acac)(CO)2组成的催化剂催化不同烯烃羰化酰胺化反应a
a Rh(acac)(CO)2 0.1mol％(0.01mmol)，含氮膦配体L1 0.05mmol，α-烯烃10.0mmol，HBF4 0.05mmol，甲醇3mL，CO/NH3(9:1)4.0MPa，120℃，24小时。
b气相色谱分析。

Claims (1)

1.一种由烯烃、一氧化碳和氨气制备一级酰胺的方法，其特征在于，在聚四氟乙烯内衬的不锈钢高压反应釜中依次加入溶剂、烯烃、铑化合物、膦配体和质子酸，充入CO和NH3混合气体，在2.0～8.0MPa总压力下，反应温度为80～150℃，反应1～24小时后，冷却至室温，泄压，分出有机相，乙醚萃取有机产品，得到一级酰胺，其收率为38～95％；其中：
所述膦配体与铑化合物的摩尔比为1～20:1；烯烃与铑化合物的摩尔比为200～2000:1；溶剂与烯烃的体积比为1～20:1；CO与NH3体积比为9:1；
所述溶剂为甲醇、乙醇或异丙醇；
所述膦配体为具有以下结构的化合物：
CN201711154996.1A 2017-11-20 2017-11-20 一种由烯烃、一氧化碳和氨气制备一级酰胺的方法 Pending CN107935878A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711154996.1A CN107935878A (zh) 2017-11-20 2017-11-20 一种由烯烃、一氧化碳和氨气制备一级酰胺的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711154996.1A CN107935878A (zh) 2017-11-20 2017-11-20 一种由烯烃、一氧化碳和氨气制备一级酰胺的方法

Publications (1)

Publication Number Publication Date
CN107935878A true CN107935878A (zh) 2018-04-20

Family

ID=61931977

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711154996.1A Pending CN107935878A (zh) 2017-11-20 2017-11-20 一种由烯烃、一氧化碳和氨气制备一级酰胺的方法

Country Status (1)

Country Link
CN (1) CN107935878A (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111718246A (zh) * 2020-07-18 2020-09-29 万华化学集团股份有限公司 一种合成γ-烷氧基醇的方法
CN113735730A (zh) * 2021-09-02 2021-12-03 广州大学 一种酰基伯胺的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1053785A (zh) * 1990-02-05 1991-08-14 国际壳牌研究有限公司 酰胺的制备
CN104926578A (zh) * 2015-04-03 2015-09-23 中国科学院兰州化学物理研究所 一种脂肪酰胺的制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1053785A (zh) * 1990-02-05 1991-08-14 国际壳牌研究有限公司 酰胺的制备
CN104926578A (zh) * 2015-04-03 2015-09-23 中国科学院兰州化学物理研究所 一种脂肪酰胺的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YANA V. FEDOTOVA ET AL.: "Phosphinohydrazines and phosphinohydrazides M(–N(R)–N(R)–PPh2)n of some transition and main group metals: synthesis and characterization Rearrangement of Ph2P–NR–NR– ligands into aminoiminophosphorane, RN=PPh2–NR–, and related chemistry", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111718246A (zh) * 2020-07-18 2020-09-29 万华化学集团股份有限公司 一种合成γ-烷氧基醇的方法
CN113735730A (zh) * 2021-09-02 2021-12-03 广州大学 一种酰基伯胺的制备方法
CN113735730B (zh) * 2021-09-02 2023-11-28 广州大学 一种酰基伯胺的制备方法

Similar Documents

Publication Publication Date Title
Cozzi et al. Chiral Phosphinopyrrolyl‐Oxazolines: A New Class of Easily Prepared, Modular P, N‐Ligands
Li et al. A general catalytic methylation of amines using carbon dioxide.
Xiao et al. Palladium-catalyzed three-component reaction of allenes, aryl iodides, and diazo compounds: approach to 1, 3-dienes.
Zhu et al. Well-defined NHC–Pd (II)–Im (NHC= N-heterocyclic carbene; Im= 1-methylimidazole) complex catalyzed C–N coupling of primary amines with aryl chlorides
Tan et al. Synthesis and structure of an air-stable organobismuth triflate complex and its use as a high-efficiency catalyst for the ring opening of epoxides in aqueous media with aromatic amines
Wang et al. Synthesis, structure and catalytic properties of CNN pincer palladium (II) and ruthenium (II) complexes with N-substituted-2-aminomethyl-6-phenylpyridines
Li et al. Benzimidazolium‐Pyrazole‐Palladium (II) Complexes: New and Efficient Catalysts for Suzuki, Heck and Sonogashira Reactions
KR101953211B1 (ko) 트라이덴테이트 리간드를 가지는 루테늄 카르보닐 착체를 탈수소 산화촉매로 사용해서 카르보닐기를 가지는 화합물을 제조하는 방법
Zhang et al. Zinc-mediated enantioselective addition of terminal 1, 3-diynes to N-arylimines of trifluoropyruvates
Aydemir et al. Rhodium-catalyzed transfer hydrogenation with functionalized bis (phosphino) amine ligands
Demir et al. The first used half sandwich ruthenium (II) complexes bearing benzimidazole moiety for N-alkylation of amines with alcohols
Muranaka et al. 2-Diphenylphosphanyl-4-pyridyl (dimethyl) amine as an effective ligand for the ruthenium (II) complex catalyzed homogeneous hydration of nitriles under neutral conditions
Aydemir et al. trans-and cis-Ru (II) aminophosphine complexes: Syntheses, X-ray structures and catalytic activity in transfer hydrogenation of acetophenone derivatives
Wang et al. Nickel-catalyzed highly regioselective hydrocyanation of alkenes with Zn (CN) 2
CN106513048A (zh) 用于内烯烃氢甲酰化反应的催化剂及其制备方法和应用
Goossen et al. A Practical and Effective Ruthenium Trichloride‐Based Protocol for the Regio‐and Stereoselective Catalytic Hydroamidation of Terminal Alkynes
CN107935878A (zh) 一种由烯烃、一氧化碳和氨气制备一级酰胺的方法
KR20210090657A (ko) 치환된 아미노 알콜을 제조하는 방법
Fabre et al. Generation of Alkyl (dicarbonyl)(chloro)‐ruthenium Dimers in the Ruthenium‐Catalyzed Addition of Alkyl Formates to Ethylene
Hoarau et al. New homochiral bis (oxazoline) ligands for asymmetric catalysis
Shen et al. One-pot synthesis of 4 (3H)-quinazolinones from azides, alkynes, anilines, and carbon monoxide
Liu et al. Preparation and catalytic properties of bis (imino) pyridine palladium (II) complexes as efficient catalysts for Suzuki cross‐coupling reaction in water
Liu et al. Copper-mediated electrophilic imination of alkenylzirconocenes with O-benzoyl ketoximes and aldoximes
Chapman et al. Synthesis of functionalised phenylalanines using rhodium catalysis in water
Aydemir et al. Applications of transition metal complexes containing 3, 3′-bis (diphenylphosphinoamine)-2, 2′-bipyridine ligand to transfer hydrogenation of ketones

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180420

WD01 Invention patent application deemed withdrawn after publication