铁(Ⅲ)催化氯代炔烃水化反应合成α-氯代甲基酮类化合物

doi:10.7503/cjcu20140400

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (12): 2563.doi: 10.7503/cjcu20140400

铁(Ⅲ)催化氯代炔烃水化反应合成α-氯代甲基酮类化合物

易卫国, 鄢东, 吴超, 兰立新()

湖南化工职业技术学院制药与生物工程系, 株洲 412004

收稿日期:2014-04-25 出版日期:2014-12-10 发布日期:2014-11-29
作者简介:联系人简介: 兰立新, 男, 副教授, 主要从事金属催化及在生物领域的应用研究. E-mail:hnllx@126.com
基金资助:
湖南省科技厅基金(批准号: 2012FJ3039)和湖南省教育厅科学研究项目(批准号: 13C236)资助

Synthesis of α-Chloromethyl Ketones by Iron-catalyzed Hydration Reaction of Alkynyl Chlorides^†

YI Weiguo, YAN Dong, WU Chao, LAN Lixin^*()

Department of Pharmaceutical and Biological Engineering,Hunan Chemical Vocational Technology College, Zhuzhou 412004, China

Received:2014-04-25 Online:2014-12-10 Published:2014-11-29
Contact: LAN Lixin E-mail:hnllx@126.com
Supported by:
† Supported by the Department of Science and Technology Foundation of Hunan Province, China(No.2012FJ3039) and the Scientific Research Fund of Hunan Provincial Education Department, China(No.13C236)

摘要/Abstract

摘要：

研究了Fe(Ⅲ)催化氯代炔烃水化生成α-氯代甲基酮化合物的反应, 考察了催化剂的种类、酸的种类、反应温度以及溶剂对反应的影响.结果表明, 采用FeCl₃·6H₂O(摩尔分数5%)和甲基磺酸(摩尔分数20%), 在1,2-二氯乙烷溶剂中, 氯代炔烃于80 ℃进行水化反应3 h, 可以高产率得到α-氯代甲基酮产物. 所得化合物的结构采用IR, ¹H NMR, ¹³C NMR及MS等方法进行了表征. 该水化反应合成方法简单、条件温和且收率良好, 为合成α-氯代甲基酮提供了一种简便途径.

关键词: 铁催化, 炔基氯, α-氯代酮, 水化反应

Abstract:

α-Chloro-methyl ketones are among the most versatile intermediates in organic synthesis, and their high reactivity makes them prone to react with a large number of nucleophiles to provide a variety of useful compounds. Hydration of alkynes has emerged as a powerful method for synthesizing carbonyl compounds because of its atom efficiency and its environmental advantages. A novel iron-catalyzed hydration reaction of alkynyl chlorides to synthesize α-chloro-methyl ketones was developed. The influences of catalyst, acid, reaction temperature and solvent were investigated, the result indicated that the reaction proceeded smoothly to give the corresponding products in good yields using 5%(molar fraction) FeCl₃·6H₂O, 20%(molar fraction) MsOH and H₂O in 1,2-dichloroethane(DCE) for 3 h at 80 ℃. The structure of α-chloromethyl ketone derivatives was confirmed by IR, ¹H NMR, ¹³C NMR and MS. The reaction method with its advantages of simple procedure, mild reaction conditions and high yield provides a novel valuable approach to α-chloro-methyl ketones.

Key words: Iron catalysis, Alkynyl chloride, α-Chloromethyl ketone, Hydration reaction

中图分类号:

O621

TrendMD:

易卫国, 鄢东, 吴超, 兰立新. 铁(Ⅲ)催化氯代炔烃水化反应合成α-氯代甲基酮类化合物. 高等学校化学学报, 2014, 35(12): 2563.

YI Weiguo, YAN Dong, WU Chao, LAN Lixin. Synthesis of α-Chloromethyl Ketones by Iron-catalyzed Hydration Reaction of Alkynyl Chlorides^†. Chem. J. Chinese Universities, 2014, 35(12): 2563.

图/表 3

参考文献 21

[1]	Erian A., Sherif S., Gaber H., Molecules,2003, 8(11), 793—865
[2]	Ji Y. F., Chen T. M., Mao H. F., Zou J. P., Chem. Res. Chinese Universities, 2012, 28(4), 642—646
[3]	Rogeli R., William R. D., Tetrahedron,2004, 60(42), 9325—9374
[4]	Prakash G. S., Ismail R., Garcia J., Tetrahedron Lett., 2011, 52(11), 1217—1221
[5]	Erian A. W., J. Heterocycl. Chem., 2001, 38(4), 793—808
[6]	Clibbens D. A., Nierenstein M., J. Chem. Soc. Trans., 1915, 107, 1491—1491
[7]	Nebot J., Romea P., Urpí F., J. Org. Chem., 2009, 74(19), 7518—7521
[8]	Wang B. G., Yu S. C., Chai X. Y., Yan Y. Z., Hu H. G., Wu Q. Y., Chin. Chem. Lett., 2011, 22(5), 519—522
[9]	Baidossi W., Lahav M., Blum J., J. Org. Chem., 1997, 62(3), 669—672
[10]	Suzuki T., Tokunaga M., Wakatsuki Y., Org. Lett., 2001, 3(5), 735—737
[11]	Liu K. J., Chem. J. Chinese Universities, 2014, 35(6), 1236—1240
	(刘开建. 高等学校化学学报, 2014, 35(6), 1236—1240)
[12]	Wessig P., Teubner J.,Synlett., 2006, (10), 1543—1546
[13]	Thuong M. B. T., Mann A., Wagner A., Chem. Commun., 2012, 48, 434—436
[14]	Tachinami T., Nishimura T., Ushimaru R., Noyori R., Naka H., J. Am. Chem. Soc., 2012, 135(1), 50—53
[15]	Wu X. F., Bezier D., Darcel C., Adv. Synth. Catal., 2009, 351(3), 367—370
[16]	Park J., Yeon J., Lee P. H., Lee K., Tetrahedron Lett., 2013, 54(33), 4414—4417
[17]	Sud D., Wigglesworth T. J., Branda N. R., Angew. Chem. Int. Ed., 2007, 46(42), 8017—8019
[18]	Ram R. N., Manoj T. P., J. Org. Chem., 2008, 73(14), 5633—5635
[19]	Burkamp F., Fletcher S. R., J. Heterocycl. Chem., 2002, 39(6), 1177—1187
[20]	He W. M., Xie L. Y., Xu Y. Y., Xiang J. N., Zhang L. M., Org. Biomol. Chem., 2012, 10, 3168—3171
[21]	Bras G. L., Provot O., Peyrat J., Alami M., Brion J., Tetrahedron Lett., 2006, 47(31), 5497—5501

Compd.	MS(ES⁺), m/z(ref.)	Compd.	MS(ES⁺), m/z(ref.)	Compd.	MS(ES⁺), m/z(ref.)
2a	154.0(154.0^[18])	2g	168.0(168.0^[20])	2m	164.1(164.1^[20])
2b	168.0(168.0^[18])	2h	240.1(240.1^[19])	2n	303.1(303.1^[20])
2c	188.0(188.0^[18])	2i	250.1(250.1^[19])	2o	279.1(279.1^[20])
2d	231.9(231.9^[18])	2j	214.0(214.0^[19])	2p	160.1(160.1^[19])
2e	182.0(182.0^[18])	2k	304.1(304.1^[19])	2q	212.0(212.0^[20])
2f	218.1(218.1^[19])	2l	192.1(192.1^[19])	2r	262.1(262.1^[20])

Compd.	MS(ES⁺), m/z(ref.)	Compd.	MS(ES⁺), m/z(ref.)	Compd.	MS(ES⁺), m/z(ref.)
2a	154.0(154.0^[18])	2g	168.0(168.0^[20])	2m	164.1(164.1^[20])
2b	168.0(168.0^[18])	2h	240.1(240.1^[19])	2n	303.1(303.1^[20])
2c	188.0(188.0^[18])	2i	250.1(250.1^[19])	2o	279.1(279.1^[20])
2d	231.9(231.9^[18])	2j	214.0(214.0^[19])	2p	160.1(160.1^[19])
2e	182.0(182.0^[18])	2k	304.1(304.1^[19])	2q	212.0(212.0^[20])
2f	218.1(218.1^[19])	2l	192.1(192.1^[19])	2r	262.1(262.1^[20])

Entry		Yield^b(%)	Entry		Yield^b(%)
1	2b	90	10	2k	83
2	2c	95	11	2l	85
3	2d	93	12	2m	81
4	2e	82	13	2n	81
5	2f	88	14	2o	78
6	2g	91	15	2p	90
7	2h	85	16	2q	88
8	2i	88	17	2r	84
9	2j	87

Entry		Yield^b(%)	Entry		Yield^b(%)
1	2b	90	10	2k	83
2	2c	95	11	2l	85
3	2d	93	12	2m	81
4	2e	82	13	2n	81
5	2f	88	14	2o	78
6	2g	91	15	2p	90
7	2h	85	16	2q	88
8	2i	88	17	2r	84
9	2j	87

铁(Ⅲ)催化氯代炔烃水化反应合成α-氯代甲基酮类化合物

Synthesis of α-Chloromethyl Ketones by Iron-catalyzed Hydration Reaction of Alkynyl Chlorides^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 3

参考文献 21

相关文章 5

编辑推荐

Metrics

本文评价

Entry	Catalyst	Acid	Solvent	Temperature/℃	Time/h	Yield^b (%)
1	FeCl₃	—	DCE	80	24	34
2	FeCl₃	TsOH	DCE	80	8	67
3	FeCl₃	MsOH	DCE	80	8	78
4	FeCl₃	TFA	DCE	80	8	58
5	FeCl₃	TfOH	DCE	80	8	77
6	FeCl₃	HNTf₂	DCE	80	8	40
7	FeCl₃	MsOH	DCE	80	3	81
8	FeBr₃	MsOH	DCE	80	3	66
9	FeCl₃·6H₂O	MsOH	DCE	80	3	88^c
10	Fe(acac)₃	MsOH	DCE	80	3	72
11	FeCl₂	MsOH	DCE	80	3	77
12	FeBr₂	MsOH	DCE	80	3	70
13	FeSO₄·7H₂O	MsOH	DCE	80	3	61
14	Fe(OAc)₂	MsOH	DCE	80	3	64
15	FeCl₃·6H₂O	MsOH	DCE	r.t.	3	47
16	FeCl₃·6H₂O	MsOH	DCE	50	3	71
17	FeCl₃·6H₂O	MsOH	THF	80	3	21
18	FeCl₃·6H₂O	MsOH	CH₃CN	80	3	65
19	FeCl₃·6H₂O	MsOH	Toluene	80	3	28
20	FeCl₃·6H₂O	MsOH	1,4-Dioxane	80	3	53

Entry		Yield^b(%)	Entry		Yield^b(%)
1	2b	90	10	2k	83
2	2c	95	11	2l	85
3	2d	93	12	2m	81
4	2e	82	13	2n	81
5	2f	88	14	2o	78
6	2g	91	15	2p	90
7	2h	85	16	2q	88
8	2i	88	17	2r	84
9	2j	87

Entry		Yield^b(%)	Entry		Yield^b(%)
1	2b	90	10	2k	83
2	2c	95	11	2l	85
3	2d	93	12	2m	81
4	2e	82	13	2n	81
5	2f	88	14	2o	78
6	2g	91	15	2p	90
7	2h	85	16	2q	88
8	2i	88	17	2r	84
9	2j	87

[1]	张维中,温月丽,宋镕鹏,王斌,张倩,黄伟. 催化剂表面Cu⁰含量对二氧化碳加氢合成C₂₊醇性能的影响[J]. 高等学校化学学报, 2020, 41(6): 1297.
[2]	王莹钰, 赵怀远, 侯昭胤. Fe₂O₃/rGO/N-rGO催化剂的制备及在硝基苯选择性加氢中的应用[J]. 高等学校化学学报, 2018, 39(8): 1750.
[3]	郑遗凡, 刘化章, 李小年. 熔铁催化剂还原过程的原位XRD研究及活性相的形成机理[J]. 高等学校化学学报, 2009, 30(6): 1177.
[4]	钟永科, 李桂英, 祝良芳, 唐典勇, 胡常伟 . 活性炭载铁催化剂作用下几种典型芳烃一步氧化羟基化反应研究[J]. 高等学校化学学报, 2007, 28(8): 1570.
[5]	李利东, 王齐, 范志强. 铁系后过渡金属催化剂/不同铝氧烷体系制备具有双峰分子量分布的聚乙烯[J]. 高等学校化学学报, 2004, 25(9): 1777.

Entry		Yield^b(%)	Entry		Yield^b(%)
1	2b	90	10	2k	83
2	2c	95	11	2l	85
3	2d	93	12	2m	81
4	2e	82	13	2n	81
5	2f	88	14	2o	78
6	2g	91	15	2p	90
7	2h	85	16	2q	88
8	2i	88	17	2r	84
9	2j	87

Entry		Yield^b(%)	Entry		Yield^b(%)
1	2b	90	10	2k	83
2	2c	95	11	2l	85
3	2d	93	12	2m	81
4	2e	82	13	2n	81
5	2f	88	14	2o	78
6	2g	91	15	2p	90
7	2h	85	16	2q	88
8	2i	88	17	2r	84
9	2j	87

铁(Ⅲ)催化氯代炔烃水化反应合成α-氯代甲基酮类化合物

Synthesis of α-Chloromethyl Ketones by Iron-catalyzed Hydration Reaction of Alkynyl Chlorides†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 3

参考文献 21

相关文章 5

编辑推荐

Metrics

本文评价

Synthesis of α-Chloromethyl Ketones by Iron-catalyzed Hydration Reaction of Alkynyl Chlorides^†

Entry		Yield^b(%)	Entry		Yield^b(%)
1	2b	90	10	2k	83
2	2c	95	11	2l	85
3	2d	93	12	2m	81
4	2e	82	13	2n	81
5	2f	88	14	2o	78
6	2g	91	15	2p	90
7	2h	85	16	2q	88
8	2i	88	17	2r	84
9	2j	87

Entry		Yield^b(%)	Entry		Yield^b(%)
1	2b	90	10	2k	83
2	2c	95	11	2l	85
3	2d	93	12	2m	81
4	2e	82	13	2n	81
5	2f	88	14	2o	78
6	2g	91	15	2p	90
7	2h	85	16	2q	88
8	2i	88	17	2r	84
9	2j	87