广西师范大学学报（自然科学版） ›› 2022, Vol. 40 ›› Issue (4): 154-161.doi: 10.16088/j.issn.1001-6600.2021061103

• 研究论文 • 上一篇    下一篇

1,3-二溴丙烷与醇羧酸和胺一锅法生成烯丙基化合物

阴玉栋1,2, 柯善喆1,2, 黄家艳1,2, 邓梦湘1,2, 刘观艳1,2, 程克光1,2*   

  1. 1. 省部共建药用资源化学与药物分子工程国家重点实验室(广西师范大学),广西桂林 541004;
    2. 广西师范大学化学与药学学院,广西桂林 541004
  • 发布日期:2022-08-05
  • 通讯作者: 程克光 (1983—),女,湖北荆州人,广西师范大学教授,博士。E-mail:kgcheng2008@gmail.com
  • 基金资助:
    国家自然科学基金(21562006);广西自然科学基金(2013GXNSFBA019184);2012年度广西教育厅科研项目(201202ZD008);药用资源化学与药物分子工程教育部重点实验室资助课题(CMEMR2012-B03,CMEMR2013-A01);广西师范大学校级重点项目(2010ZD008)

One-pot Generation of Allylated Products from Alcohols, Carboxylic Acids and Amines with 1,3-Dibromopropane by Sodium Hydride

YIN Yudong1,2, KE Shanzhe1,2, HUANG Jiayan1,2, DENG Mengxiang1,2, LIU Guanyan1,2, CHENG Keguang1,2*   

  1. 1. State Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Guangxi Normal University),Guilin Guangxi 541004, China;
    2. School of Chemistry and Pharmacy, Guangxi Normal University, Guilin Guangxi 541004, China
  • Published:2022-08-05

PDF (PC)

96

摘要： 将1,3-二溴丙烷与醇、羧酸和胺反应得到烯丙基化合物。本文运用“一锅法”策略,首先以雌二醇为原料在碱作用下与1,3-二溴丙烷反应,并考察此烯丙基化反应的最佳条件,之后在最佳条件下将其他醇、羧酸和胺替代雌二醇进行反应。实验结果显示,雌二醇与1,3-二溴丙烷在NaH作用下反应得到3,17β-二烯丙氧基雌二醇-1,3,5(10)-三烯而非3-溴丙基衍生物。因此,1,3-二溴丙烷与其他醇、羧酸和胺的“一锅法”反应可在温和条件下以较高产率得到烯丙醚、烯丙酯和烯丙胺。

关键词: 烯丙基醚, 烯丙基化, 1,3-二溴丙烷, 氢化钠, 一锅法

Abstract: 1,3-Dibromopropane was reacted with alcohol, carboxylic acid and amine respectively to obtain a series of allyl compounds. The one-pot approach was used in this study. Firstly, estradiol as a raw material reacted with 1,3-dibromopropane under the action of alkali then the best conditions for this allylation reaction were determined. Under the best conditions, estradiol was replaced with other alcohols, carboxylic acids and amines for the reaction. The experimental results showed that the reaction of estradiol and 1,3-dibromopropane under the action of NaH alkali produced 3,17β-diallyloxyestradiol-1,3,5(10)-triene instead of 3-bromopropyl. The reaction of 1,3-dibromopropane with other alcohols, carboxylic acids and amines got higher yield of allyl ethers, allyl esters and allylamines under relatively mild conditions.

Key words: allyl ether, allylation, 1,3-dibromopropane, sodium hydride, one-pot

中图分类号: 

  • O621.3
[1] 韩博士, 时郑, 何慧红, 等. 铜催化芳基(或烷基)卤化物选择性烯丙基化反应研究[J]. 有机化学, 2021, 41(2): 695-701. DOI: 10.6023/cjoc202008012.
[2]ARISTIZABAL L, NGEL M, OROZCO C, et al. Computational study of the thermal decomposition and the thermochemistry of allyl ethers and allyl sulfides[J]. Structural Chemistry, 2018, 29(3): 897-907. DOI: 10.1007/s11224-018-1074-8.
[3]SABERIAN M, JAVAHERIAN N H. Synthesis of allyl ether and benzyl methacrylate functionalized silane monomers for application in acrylate/montmorillonite nanocomposite emulsion[J]. Journal of Adhesion Science and Technology, 2020, 34(2): 153-166. DOI: 10.1080/01694243.2019.1662203.
[4]KON Y, FUJITANI T, NAKASHIMA T, et al. Versatile etherification of alcohols with allyl alcohol by a titanium oxide-supported molybdenum oxide catalyst: gradual generation from titanium oxide and molybdenum oxide[J].Catalysis Science and Technology, 2018, 8(18): 4618-4625. DOI: 10.1039/C8CY00613J.
[5]YADA A, NISHI S, SATO Y, et al. Palladium-catalyzed dehydrogenative coupling reaction of terminal alkynes with unactivated alkenes[J].Journal of the Chinese Chemical Society, 2018, 65(1): 117-121. DOI: 10.1002/jccs.201700268.
[6]黄婉云, 殷鹏龙, 李虹, 等. 喹诺酮-二茂铁杂合物的合成及生物活性研究[J]. 广西师范大学学报(自然科学版), 2016, 34(2): 111-115. DOI: 10.16088/j.issn.1001-6600.2016.02.016.
[7]梁晓龙, 黄婉云, 潘成学, 等. 5-乙酰胺基-4-(4-氯苯基)-2-甲基-6-氧代-5,6-二氢-4H-吡喃-3-羧酸乙酯的合成及晶体结构[J]. 广西师范大学学报(自然科学版), 2015, 33(2): 82-87. DOI: 10.16088/j.issn.1001-6600.2015.02.013.
[8]CHEN W H, LI Y, CHEN Y, et al. (NHC)NiH-catalyzed regiodivergent cross-hydroalkenylation of vinyl ethers with α-olefins: syntheses of 1,2-and 1,3-disubstituted allyl ethers[J]. Angewandte Chemie International Edition, 2018, 57(10): 2677-2681. DOI: 10.1002/anie.201712693.
[9]TSAI M S, RAO U N, WANG J R, et al. Triphenylphosphine-mediated reduction of electron-deficient propargyl ethers to the allylic ethers[J].Journal of the Chinese Chemical Society, 2001, 48(5): 869-876. DOI: 10.1002/jccs.200100126.
[10]CHOUDHARY U, MIR A A, EMRICK T. Soluble, allyl-functionalized deoxybenzoin polymers[J].Macromolecules, 2017, 50(10): 3772-3778. DOI: 10.1021/acs.macromol.7b00460.
[11]KELLY C B, OVIAN J M, CYWAR R M, et al. Oxidative cleavage of allyl ethers by an oxoammonium salt[J]. Organic and Biomolecular Chemistry, 2015, 13(14): 4255-4259. DOI: 10.1039/c5ob00270b.
[12]TANAKA S, SUZUKI Y, KIMURA T, et al. Achiral picolinic acid ligand, Cl-Naph-PyCOOH, for CpRu-catalyzed dehydrative allylation: design, synthesis, and properties[J].Bulletin of the Chemical Society of Japan, 2019, 92(10): 1707-1720. DOI: 10.1246/bcsj.20190134.
[13]HE R, HUO X H, ZHAO L, et al. Stereodivergent Pd/Cu catalysis for the dynamic kinetic asymmetric transformation of racemic unsymmetrical 1,3-disubstituted allyl acetates[J].Journal of the American Chemical Society, 2020, 142(18): 8097-8103. DOI: 10.1021/jacs.0c02150.
[14]NAKAGAWA H, HIRABAYASHI T, SAKAGUCHI S, et al. Allylation of alcohols and carboxylic acids with allyl acetate catalyzed by [Ir(cod)2]+BF-4complex[J].Journal of Organic Chemistry, 2004, 69(10): 3474-3477. DOI: 10.1021/jo049828k.
[15]KAYAKI Y, KODA T, IKARIYA T, Halide-free dehydrative allylation using allylic alcohols promoted by a palladium-triphenyl phosphite catalyst[J].Journal of Organic Chemistry, 2004, 69(7): 2595-2597. DOI: 10.1021/jo030370g.
[16]KIM H, LEE C. A mild and efficient method for the stereoselective formation of C-O bonds: palladium-catalyzed allylic etherification using zinc(II) alkoxides[J].Organic Letters, 2002, 4(24): 4369-4371. DOI: 10.1021/ol027104u.
[17]罗源军. 八氟戊基烯丙基醚的制备与结构表征[J]. 化工生产与技术, 2019, 25(1): 4-7. DOI: 10.3969/j.issn.1006-6829.2019.01.002.
[18]房连顺, 董晓红. 乙二醇单烯丙基醚的合成[J]. 精细与专用化学品, 2017, 25(1): 37-40. DOI: 10.19482/j.cn11-3237.2017.01.07.
[19]WILLIAMSON A W. XXII. On etherification[J]. Quarterly Journal of the Chemical Society of London, 1852, 4(3): 229-239. DOI: 10.1039/QJ8520400229.
[20]刘观艳, 程克光, 邓胜平, 等. 雌二醇酯类衍生物的合成与抗肿瘤活性研究[J]. 广西师范大学学报(自然科学版), 2013, 31(1): 62-66. DOI: 10.16088/j.issn.1001-6600.2013.01.008.
[21]孙立,初相伍,刘春梅,等. 熊果酸/甘草次酸-尿嘧啶核苷缀合物的合成与抗肿瘤活性评价[J].广西师范大学学报(自然科学版),2020,38(1):87-92.DOI: 10.16088/j.issn.1001-6600.2020.01.011.
[22]刘晶晶, 陈转欣, 尤佳航, 等. 齐墩果酸-对羟基苯甲腈及其类似物的合成与抗肿瘤活性评价[J]. 广西师范大学学报(自然科学版), 2021, 39(2): 132-138. DOI: 10.16088/j.issn.1001-6600.2020011603.
[23]KVASNICA M, RAROVA L, OKLESTKOVA J, et al. Synthesis and cytotoxic activities of estrone and estradiol cis-dichloroplatinum (II) complexes[J]. Bioorganic and Medicinal Chemistry, 2012, 20(24): 6969-6978. DOI: 10.1016/j.bmc.2012.10.013.
[24]SCHWARZ S, WEBER G. Esterification of phenolic hydroxyl groups in steroids:Germany,DD120016[P]. 1976-05-20.
[25]MALLAVADHANI U V, MAHAPATRA A, PATTNAIK B, et al. Synthesis and anti-cancer activity of some novel C-17 analogs of ursolic and oleanolic acids[J]. Medicinal Chemistry Research, 2013, 22(3): 1263-1269. DOI: 10.1007/s00044-012-0106-y.
[26]BENEDETTO E, TREDWELL M, HOLLINGWORTH C, et al. Regio-and stereoretentive synthesis of branched, linear (E)-and (Z)-allyl fluorides from allyl carbonates under Ir-catalysis[J].Chemical Science, 2013, 4(1): 89-96. DOI: 10.1039/c2sc21789a.
[27]DELANY E G, FAGAN C L, GUNDALA S, et al. Aerobic oxidation of NHC-catalysed aldehyde esterifications with alcohols: benzoin, not the Breslow intermediate, undergoes oxidation[J]. Chemical Communications, 2013, 49(58): 6513-6515. DOI: 10.1039/c3cc42597e.
[28]KIMURA M, FUTAMATA M, SHIBATA K, et al. Pd·Et3B-catalyzed alkylation of amines with allylic alcohols[J].Chemical Communications, 2003(2): 234-235. DOI: 10.1039/b210920d.
[29]TAO Y S, WANG B, WANG B M, et al. Highly efficient and regioselective allylation with allylic alcohols catalyzed by [Mo3S4Pd(η3-allyl)] clusters[J].Organic Letters, 2010, 12(12): 2726-2729. DOI: 10.1021/ol100805c.
[30]YANG S C, HUNG C W. An efficient palladium-catalyzed route to N-allylanilines by the direct use of allyl alcohols[J]. Synthesis, 1999, 1999(10): 1747-1752. DOI: 10.1055/s-1999-3584.
[31]FUJI M, CHIWATA J, OZAKI M, et al. In Situ generated niobium-catalyzed synthesis of 3-pyrroline derivatives via ring-closing metathesis reactions[J]. ACS Omega, 2018, 3(8): 8865-8873. DOI: 10.1021/acsomega.8b01642.
[32]SCHMIDT B, KREHL S, JABLOWSKI E. Assisted tandem catalytic RCM-aromatization in the synthesis of pyrroles and furans[J]. Organic and Biomolecular Chemistry, 2012, 10(26): 5119-5130. DOI: 10.1039/c2ob25543j.
[1] 花世鲜, 王迎春, 李亚军, 王恒山. 脱氢松香基12位芳基取代衍生物的合成与光学性质[J]. 广西师范大学学报（自然科学版）, 2013, 31(2): 64-68.
Viewed
Full text


Abstract

Cited
  Shared   
  Discussed   
No Suggested Reading articles found!
版权所有 © 广西师范大学学报（自然科学版）编辑部
地址：广西桂林市三里店育才路15号　邮编：541004
电话：0773-5857325　E-mail: gxsdzkb@mailbox.gxnu.edu.cn
本系统由北京玛格泰克科技发展有限公司设计开发