甲基三氧化铼催化合成罗汉柏木烷酮

doi:10.3969/j.issn.0253-2417.2021.04.004

Abstract

Abstract:

Thujopsanone was synthesized by oxidation reaction with thujopsene as raw material, dichloromethane as solvent, methyltrioxorhenium(MTO) as catalyst, 30% H₂O₂ as oxidant, and 3-methylpyrazole as co-catalyst. The effects of reaction conditions on the oxidation were studied. The optimized reaction were obtained as follows: the reaction temperature 30℃, the molar ratio of raw materals(n(H₂O₂): n(thujopsene)) 1:1, the reaction time 3 h, the catalyst amounts 0.3%(based on the weight of thujopsene, similarly hereinafter), the dosage of 3-methylpyrazole is 10%. Under these conditions, the yield of thujopsanone was 72.1%, and the conversion rate of thujopsene was 97.3%. The structure of the products was identified by GC-MS and FT-IR, and it was confirmed as wasthujopsanone.

Key words: thujopsanone, MTO, oxidation, thujopsene, 3-methylpyrazole

CLC Number:

TQ35

Sheng ZHANG, Kai ZHU. Synthesis of Thujopsanone Catalyzed by Methyltrioxorhenium[J]. Chemistry and Industry of Forest Products, 2021, 41(4): 23-28.

Figures/Tables 6

Fig.1

Fig.2

Fig.3

Table 1

Fig.4

Fig.5

References 18

1	SHRINIVAS P , HERBERT C . Hydroboration of terpenes.Ⅶ: Hydroboration of (-)-thujopsene configurations of the isomeric 3-thujopsanoIs and 3-thujopsanones[J]. Journal of Organic Chemistry, 1970, 35 (11): 3874- 3879. doi: 10.1021/jo00836a064
2	OHLOFF G , STRICKLER H , WILLHALM B , et al. Vberen-synthesenmitsingulett-sauerstoff Ⅱ: Die farbstoff-sensibilisiertephotooxygenierung von (-)-thujopsene und die stereochemie der dargestelltenthujopsanole[J]. Helvetica Chimica Acta, 1970, 53 (3): 623- 637. doi: 10.1002/hlca.19700530321
3	PANTEN J , BERTRAM H J , SURBURG H . New woody and ambery notes from cedarwood and turpentine oil[J]. Chemistry and Biodosimetry, 2004, 1 (12): 1936- 1948.
4	叶剑飞. 罗汉柏木烯的异构化[D]. 杭州: 浙江大学, 2003.
	YE J F. Isomerization of thujopsene[D]. Hangzhou: Zhejiang University, 2003.
5	LIN Z , AHMED A A , RICHARD F H , et al. (+)-Dihydromayurone from juniperusoccidentails[J]. Planta Medica, 1999, (65): 680- 681.
6	续艳, 刘六军, 何亮. 多聚磷酸催化罗汉柏木烯异构化反应工艺[J]. 西北林学院学报, 2014, 29 (3): 171- 173. doi: 10.3969/j.issn.1001-7461.2014.03.34
	XU Y , LIU L J , HE L . Polyphosphoric acid catalyzed isomerization reaction process of thujopsene[J]. Journal of Northwest Forestry University, 2014, 29 (3): 171- 173. doi: 10.3969/j.issn.1001-7461.2014.03.34
7	郭诗平. 柏木烯催化异构化研究[D]. 杭州: 浙江大学, 2013.
	GUO S P. Study on catalytic isomerization of cedar[D]. Hangzhou: Zhejiang University, 2013.
8	陈华成. 环氧柏木烷的合成研究[D]. 南京: 南京林业大学, 2006.
	CHEN H C. Study on the synthesis of epoxy cypress[D]. Nanjing: Nanjing Forestry University, 2006.
9	续艳, 刘六军, 何亮. 罗汉柏木烯异构化反应工艺[J]. 东北林业大学学报, 2013, (6): 124- 125.
	XU Y , LIU L J , HE L . The isomerization technology of thujopsene[J]. Journal of Northeast Forestry University, 2013, (6): 124- 125.
10	吴辉平. 固体酸催化合成甲基柏木酮的研究[D]. 杭州: 浙江大学, 2010.
	WU H P. Study on catalytic synthesis of methyl chlorocetone with solid acid catalyst[D]. Hangzhou: Zhejiang University, 2010.
11	陈君, 王也, 朱凯. 阳离子树脂催化罗汉柏木烯异构化的研究[J]. 应用化工, 2018, 47 (3): 456- 459. doi: 10.3969/j.issn.1671-3206.2018.03.009
	CHEN J , WANG Y , ZHU K . Cationic resin catalyzed the isomerization of thujopsene[J]. Applied Chemical Industry, 2018, 47 (3): 456- 459. doi: 10.3969/j.issn.1671-3206.2018.03.009
12	BICH C , ANNIE F , CATHERINE G , et al. Friedel-crafts acylation of toluene and p-xylene with carboxylie acids catalyzed by zeolites[J]. Journal of Organic Chemistry, 1986, 51 (11): 2128- 2130. doi: 10.1021/jo00361a039
13	林惠琼, 张明全. 过氧乙酸制备方法与其稳定性的关系[J]. 中华消毒杂志, 2003, 20 (1): 17- 19.
	LIN H Q , ZHANG M Q . Relationship between preparation method of peracetic acid and its stability[J]. Chinese Journal of Disinfection, 2003, 20 (1): 17- 19.
14	高宇, 张月成, 赵继全. 双氮席夫碱配体对甲基三氧化铼催化烯烃环氧化反应的影响[J]. 催化学报, 2009, 30 (12): 1243- 1247. doi: 10.3321/j.issn:0253-9837.2009.12.011
	GAO Y , ZHANG Y C , ZHAO J Q . Effect of dinitrogen schiff base ligand on the epoxidation of alkenes catalyzed by methyl rhenium[J]. Chinese Journal of Catalysis, 2009, 30 (12): 1243- 1247. doi: 10.3321/j.issn:0253-9837.2009.12.011
15	刘晓莉, 张月成, 高宇. MCM-41负载甲基三氧化铼的制备及其对环氧化反应的催化性能[J]. 分子催化, 2012, (3): 239- 245.
	LIU X L , ZHANG Y C , GAO Y . Preparation of MCM-41 supported methyl rhenium trioxide and its catalytic performance for epoxidation[J]. Journal of Molecular Catalysis, 2012, (3): 239- 245.
16	臧树良, 岳爽. 新型高效催化剂-甲基三氧化铼(MTO)的研究发展[J]. 当代化工, 2007, (6): 551- 556. doi: 10.3969/j.issn.1671-0460.2007.06.001
	ZANG S L , YUE S . The research and development of a new high-efficiency catalyst-methyl rhenium trioxide(MTO)[J]. Contemporary Chemical Industry, 2007, (6): 551- 556. doi: 10.3969/j.issn.1671-0460.2007.06.001
17	SANTI C , LORENZO R D , TIDEI C , et al. Stereoselective selenium catalyzed dihydroxylation and hydroxymethoxylation of alkenes[J]. Tetrahedron, 2012, 68 (51): 10530- 10535. doi: 10.1016/j.tet.2012.08.078
18	YAROVAYA O I , POLOVINKA M P , KORCHAGINA D V , et al. Acid-catalyzed rearrangements of (-)-thujopsene[J]. Russian Journal of Organic Chemistry, 2001, 37 (3): 362- 374.

试验号 No.	A 反应温度/℃ temp.	B n(H₂O₂)∶n(罗汉柏木烯) n(H₂O₂)∶n(thujopsene)	C 3-甲基咪唑用量/% 3-methylpyrazole amount	D 催化剂用量/% catalyst amount	E 反应时间/h time	得率/% yield
1	20	1	2.5	0.2	2	24.6
2	20	2	5.0	0.3	3	68.8
3	20	3	7.5	0.4	4	67.4
4	20	4	10.0	0.5	5	52.9
5	30	1	5.0	0.4	5	47.9
6	30	2	2.5	0.5	4	25.7
7	30	3	10.0	0.2	3	71.3
8	30	4	7.5	0.3	2	70.2
9	40	1	7.5	0.5	3	57.6
10	40	2	10.0	0.4	2	65.3
11	40	3	2.5	0.3	5	21.3
12	40	4	5.0	0.2	4	46.4
13	50	1	10.0	0.3	4	60.5
14	50	2	7.5	0.2	5	43.7
15	50	3	5.0	0.5	2	27.3
16	50	4	2.5	0.4	3	21.7
k₁	53.4	47.7	23.3	46.5	46.9
k₂	53.8	50.9	47.6	55.2	54.8
k₃	47.7	46.8	59.7	50.6	50.0
k₄	38.3	47.9	62.5	40.9	41.5
R	15.5	4.1	39.1	14.3	13.4

[1]	Hao ZHOU, Xingying XUE, Hongxia CHEN, Jianzhong YE, Chengzhang WANG. Preparation of Nanoemulsion of Lacquer Seed Oil and Its Anti-oxidation and Anti-UV Activity [J]. Chemistry and Industry of Forest Products, 2021, 41(1): 45-52.
[2]	Yunfei SHI,Hui ZHANG,Xuyang ZHONG,Xinying DUAN,Shulan CHEN,Shengliang LIAO. The Optimization of Synthesis Process of Nopinone [J]. Chemistry and Industry of Forest Products, 2020, 40(2): 125-130.
[3]	JI Dexian, LIN Zhaoyun, XIA Yuanyuan, YANG Guihua, CHEN Jiachuan. Preparation of NCC Assisted NaClO Oxidized Starch and Its Influence on the Properties ofComposite Film [J]. Chemistry and Industry of Forest Products, 2019, 39(5): 33-40.
[4]	Yan PENG,Kehua TANG,Aiwen DONG. Purification of Bletilla striata Polyphenols by Macroporous Resin and Its Antioxidant Activities in Vitro [J]. Chemistry and Industry of Forest Products, 2019, 39(4): 91-99.
[5]	Jing ZHOU,Yuhao GUI,Shengzhao GONG. Antioxidant Activity of Tea Seed Shell Fermentation Extracts and Its Inhibitory Effect on Intracellular Oxidative Damage [J]. Chemistry and Industry of Forest Products, 2019, 39(4): 105-112.
[6]	ZHANG Fei, HU Yun, LIU Chengguo, ZHOU Yonghong. Synthesis and Characterization of Hydroxylated Woody Oil [J]. Chemistry and Industry of Forest Products, 2018, 38(6): 27-32.
[7]	WANG Congcong, MO Lihuan, YANG Zhen, LI Jun, XU Jun, TAN Jinqiang. Catalytic Ozonation Advanced Treatment of Pulping Effluent Catalyzed by γ-Al₂O₃ Loaded with Binary Metal Oxides [J]. Chemistry and Industry of Forest Products, 2017, 37(6): 56-64.
[8]	YAO Fengqi, TAO Junjun, WANG Haihui, HU Guoqing, CHEN Shuai, TAHIR Mudassir Hussian. Study of Pyrolysis Behavior and Reaction Mechanism of Tea Polyphenols [J]. Chemistry and Industry of Forest Products, 2017, 37(5): 19-27.
[9]	ZHENG Minrui, ZHANG Meng, HU Lihong, BO Caiying, ZHOU Yonghong. Synthesis and Properties of Epoxidized Tung Oil Methyl Ester from Tung Oil Methyl Ester with Quaternary Ammonium Phosphotungstate as Catalyst [J]. Chemistry and Industry of Forest Products, 2017, 37(3): 61-66.
[10]	XU Shi-chao, ZHAO Zhen-dong, BI Liang-wu, CHEN Yu-xiang, ZHU Shou-ji, LU Yan-ju, WANG Jing, GU Yan. Biomimetic Catalytic Oxidation of α-Pinene by Molecular Oxygen with Ferric Deuteroporphyrin Dimethyl Ester as Catalyst [J]. Chemistry and Industry of Forest Products, 2016, 36(6): 23-28.
[11]	WANG Hao-rong, JIANG Jian-chun, XU Jun-ming, LI Jing, LIU Peng. Epoxidation of Wilson dogwood Oil Catalyzed by Peroxy Quaternary Ammonium Borotungstate Catalyst [J]. Chemistry and Industry of Forest Products, 2016, 36(6): 71-75.
[12]	HOU Min, SUN Kang, DENG Xian-lun, XIAO Feng-long, LIN Guan-feng. Influence of Removal of Potassium from Activated Carbon by Using Oxidation-ultrasonic Method on Its Electrochemical Properties [J]. Chemistry and Industry of Forest Products, 2016, 36(4): 49-54.
[13]	HUANG Xu-juan, LIU He, SHANG Shi-bin, QI Fan. Synthesis Process of Epoxidized Dehydrated Castor Oil [J]. Chemistry and Industry of Forest Products, 2015, 35(4): 41-47.
[14]	YUAN Cheng, ZHANG Hui-fen, ZHANG Mi, WEI Xi, LI Bao-cai. New Oxidation Bleaching Technology of Deresinated Montan Wax [J]. Chemistry and Industry of Forest Products, 2015, 35(4): 97-104.
[15]	PENG Han, YANG Li-juan, XU Xu, WANG Shi-fa. Green Synthesis of Isolongifolenone [J]. Chemistry and Industry of Forest Products, 2015, 35(3): 97-103.

Synthesis of Thujopsanone Catalyzed by Methyltrioxorhenium

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 6

References 18

Related Articles 15

Recommended Articles

Metrics

Comments