3-对烯-1-磺酰胺类化合物的合成及其除草活性

doi:10.3969/j.issn.0253-2417.2022.01.006

林产化学与工业 ›› 2022, Vol. 42 ›› Issue (1): 43-50.doi: 10.3969/j.issn.0253-2417.2022.01.006

3-对烯-1-磺酰胺类化合物的合成及其除草活性

张红梅¹^,²^,³, 陈玉湘¹^,³, 徐士超¹^,³, 王婧¹^,²^,³, 蒋建新², 赵振东¹^,³^,*()

1. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室, 江苏南京 210042
2. 北京林业大学材料科学与技术学院, 北京 100083
3. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037

收稿日期:2020-12-04 出版日期:2022-02-28 发布日期:2022-03-11
通讯作者: 赵振东 E-mail:zdzhao@189.cn
作者简介:赵振东, 研究员, 博士生导师, 主要从事萜类化学、松树病虫害化学、天然产物化学、应用化学等方面的研究; E-mail: zdzhao@189.cn
张红梅(1992-), 女, 云南红河人, 博士生, 从事萜类化学转化利用等方面的研究
基金资助:
国家自然科学基金资助项目(31870557)

Synthesis and Herbicidal Activity Investigation of p-Menth-3-en-1-sulfonamide Compounds

Hongmei ZHANG¹^,²^,³, Yuxiang CHEN¹^,³, Shichao XU¹^,³, Jing WANG¹^,²^,³, Jianxin JIANG², Zhendong ZHAO¹^,³^,*()

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
2. College of Materials Science and Technology, Bejing Forestry University, Beijing 100083, China
3. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China

Received:2020-12-04 Online:2022-02-28 Published:2022-03-11
Contact: Zhendong ZHAO E-mail:zdzhao@189.cn

摘要/Abstract

摘要：

以松节油为原料合成了3-对烯-1-胺，继而以磺酰氯为磺酰化试剂、三乙胺为缚酸剂，合成了10种3-对烯-1-磺酰胺类化合物(2a~2j)。通过FT-IR、¹H NMR、¹³C NMR和LC-MS对所合成化合物的结构进行了表征，并评价了其对稗草的芽后除草活性。研究结果表明：3-对烯-1-磺酰胺类化合物的收率为60%~87%，各种结构表征图谱与化合物特征相符，表明成功合成了目标化合物。部分化合物对稗草的生长抑制作用明显，其中3-对烯-1-丙基磺酰胺(2f)的除草活性最好，对茎长和根长的半数抑制浓度(IC₅₀)值分别为0.36和0.17 mmol/L。细胞毒性试验结果表明：3-对烯-1-基磺酰胺类化合物毒性较低，对正常人脐静脉血管内皮细胞HUVEC-C和小鼠胚胎成纤维细胞BALB/C 3T3的体外增殖均无显著抑制。构效关系分析表明：含烷基的磺酰胺衍生物的除草活性明显高于含芳基的，当烷基为3个碳原子时活性最好，但是当烷基上连有吸电子基团时会减弱其活性；苯环或萘环上连有给电子基团(甲基、甲氧基)时活性比连吸电子基团(F、Cl、Br)要好。

关键词: 松节油, 3-对烯-1-胺, 植物源除草剂, 磺酰胺衍生物, 除草活性

Abstract:

Ten p-menth-3-en-1-sulfamide compounds (2a-2j) were synthesized by using turpentine as start material, sulfonyl chlorideas sulfonylation reagent, triethylamine as acid binding agent.Their structures were characterized by FT-IR, ¹H NMR, ¹³C NMR and LC-MS.The post-emergence herbicidal activities of them against Echinochloa crusgalli were evaluated.The results showed that the yields of p-menth-3-en-1-sulfamide compounds were 60%-87%.The structural characterization spectra were consistent with the compounds, indicating that the target compounds had been successfully synthesized.Some compounds showed obvious inhibition activities to the growth of E.crusgalli.Among them, p-menth-3-en-1-propyl-sulfamide (2f) showed the best herbicidal activity against E.crusgalli.And the IC₅₀ values of it against the stem and root growth of E.crusgalli were 0.36 and 0.17 mmol/L, respectively.Cytotoxicity assays results showed that p-menth-3-en-1-sulfamide compounds had no significant inhibition against cell proliferation of normal human HUVEC-C cells and mouse fibroblasts BALB/C 3T3 cells in vitro.Structure-activity relationship analysis showed that the herbicidal activity of alkyl sulfonamide derivatives was significantly higher than that of aryl groups and reached the best when the alkyl group containing three carbon atoms.However, the herbicidal activity was weakened when the alkyl group was connected with electron-absorbing groups.The herbicidal activities of benzene or naphthalene rings with electron-donating groups (methyl, methoxyl) were better than those of electron-absorbing groups (F, Cl, Br).

Key words: turpentine, p-menth-3-en-1-amine, botanical herbicides, sulfamide compounds, herbicidal activity

中图分类号:

TQ35

张红梅, 陈玉湘, 徐士超, 王婧, 蒋建新, 赵振东. 3-对烯-1-磺酰胺类化合物的合成及其除草活性[J]. 林产化学与工业, 2022, 42(1): 43-50.

Hongmei ZHANG, Yuxiang CHEN, Shichao XU, Jing WANG, Jianxin JIANG, Zhendong ZHAO. Synthesis and Herbicidal Activity Investigation of p-Menth-3-en-1-sulfonamide Compounds[J]. Chemistry and Industry of Forest Products, 2022, 42(1): 43-50.

图/表 4

图1

表1

表2

表3

参考文献 15

1	WANG Z F , SUN Z C , XIAO L , et al. Herbicidal polyketides and diketopiperazine derivatives from Penicillium viridicatum[J]. Journal of Agricultural and Food Chemistry, 2019, 67 (51): 14102- 14109. doi: 10.1021/acs.jafc.9b06116
2	HUANG D Z , ZHU S J , LAN H Y , et al. Design, synthesis and herbicidal activities of(3R, 4R)-4, 7, 7-trimethyl-6-oxabicyclo[3.2.1] octane-3, 4-diol derivatives[J]. Industrial Crops and Products, 2019, 129, 24- 34. doi: 10.1016/j.indcrop.2018.11.065
3	张梦杰, 王洋, 杨小琴, 等. 除草剂药害的预防和消减措施研究[J]. 土壤与作物, 2020, 9 (1): 1- 12.
	ZHANG M J , WANG Y , YANG X Q , et al. Research on herbicide phytotoxicity prevention and remedy approaches[J]. Soils and Crops, 2020, 9 (1): 1- 12.
4	JI Z , ZHOU F , WEI S . Synthesis and herbicidal activities of benzothiazole N, O-acetals[J]. Bioorganic & Medicinal Chemistry Letters, 2015, 25, 4065- 4068.
5	KAAB S B , LINS L , HANAFI M , et al. Cynara cardunculus crude extract as a powerful natural herbicide and insight into the mode of action of its bioactive molecules[J]. Biomolecules, 2020, 10, 209- 225. doi: 10.3390/biom10020209
6	刘坤, 王栢薪, 蒋丽红, 等. 松节油的应用研究[J]. 化工科技, 2013, 21 (5): 64- 68. doi: 10.3969/j.issn.1008-0511.2013.05.016
	LIU K , WANG B X , JIANG L H , et al. Research progress on application of turpentine[J]. Science & Technology in Chemical Industry, 2013, 21 (5): 64- 68. doi: 10.3969/j.issn.1008-0511.2013.05.016
7	GUIMARAES A G , SERAFINI M R , QUINTANS-JUNIOR L J . Terpenes and derivatives as a new perspective for pain treatment: A patent review[J]. Expert Opinion on Therapeutic Patents, 2014, 24 (3): 243- 265. doi: 10.1517/13543776.2014.870154
8	PAVELA R . Essential oils for the development of eco-friendly mosquito larvicides: A review[J]. Industrail Crops and Products, 2015, 76, 174- 187. doi: 10.1016/j.indcrop.2015.06.050
9	ZHU S J , XU S C , WANG J , et al. Synthesis and herbicidal activities of p-menth-3-en-1-amine and its Schiff base derivatives[J]. Journal of Agricultural and Food Chemistry, 2016, 64 (51): 9702- 9707. doi: 10.1021/acs.jafc.6b03977
10	ZHU S J , XU S C , YI X Q , et al. High value-added application of turpentine as a potential renewable source for the synthesis of heterocyclic schiff base derivatives of cis-1, 8-p-menthane-diamine serving as botanical herbicides[J]. Industrial Crops and Products, 2018, 115 (1): 111- 116.
11	DONG H H , XU S C , WANG J , et al. Synthesis and herbicidal application of turpentine derivative p-menthene type secondary amines as sustainable agrochemicals[J]. New Journal of Chemistry, 2020, 44, 8280- 8288. doi: 10.1039/D0NJ00583E
12	XU S C , ZENG X J , DAI S L , et al. Turpentine derived secondary amines for sustainable crop protection: Synthesis, activity evaluation and QSAR study[J]. Journal of Agricultural and Food Chemistry, 2020, 68, 11829- 11838. doi: 10.1021/acs.jafc.0c01909
13	赵青山, 付颖, 叶非. 三唑并嘧啶磺酰胺类除草剂的研究概况[J]. 植物保护, 2011, 37 (2): 14- 19. doi: 10.3969/j.issn.0529-1542.2011.02.003
	ZHAO Q S , FU Y , YE F . Study summary of triazolo[1, 5-α] pyrimidine-2-sulfonanilide herbicide[J]. Plant Protection, 2011, 37 (2): 14- 19. doi: 10.3969/j.issn.0529-1542.2011.02.003
14	石德清, 刘军安, 刘小鹏, 等. 4-芳氧乙(丙)酰氨基苯磺酰胺的合成与除草活性[J]. 应用化学, 2003, 20 (2): 130- 133.
	SHI D Q , LIU J A , LIU X P , et al. Synthesis of 4-aryloxyacetamido(propionamido)benzene-sulfonamides and their herbicidal activity[J]. Chinese Journal of Applied Chemistry, 2003, 20 (2): 130- 133.
15	董欢欢, 徐士超, 王婧, 等. 3-对烯-1-胺的合成工艺研究[J]. 林产化学与工业, 2019, 39 (5): 67- 72.
	DONG H H , XU S C , WANG J , et al. Synthetic technology of p-menth-3-en-1-amine[J]. Chemistry and Industry of Forest Products, 2019, 39 (5): 67- 72.

化合物 compound	不同浓度(mmol/L)时的茎长抑制率/% stem growth inhibition rate of different concentration							不同浓度(mmol/L)时的根长抑制率/% root growth inhibition rate of different concentration
化合物 compound	5	2.5	1.25	0.625	0.313	0.156	0.078	5	2.5	1.25	0.625	0.313	0.156	0.078
1	100.0	94.3	67.8	27.3	13.7	7.3	8.9	100.0	100.0	98.6	69.7	31.4	23.0	19.5
2a	23.6	22.6	18.3	13.8	6.4	9.4	3.4	45.0	17.6	7.3	6.4	7.1	7.8	9.0
2b	22.7	32.7	25.7	26.6	29.5	27.1	22.6	49.6	27.2	10.1	17.6	18.2	17.4	8.0
2c	22.3	17.7	16.1	15.7	12.1	6.0	2.0	22.2	19.6	6.8	7.0	9.0	0.1	2.4
2d	35.5	31.4	23.7	20.1	18.3	17.0	11.8	41.2	13.7	17.7	9.3	9.3	9.4	10.1
2e	5.8	-3.0	-0.4	-1.7	-7.6	-2.3	-0.8	13.2	11.2	9.1	6.1	4.1	6.1	4.3
2f	100.0	95.9	84.7	65.2	36.0	19.9	18.0	100.0	100.0	96.1	86.4	60.7	44.2	31.5
2g	40.3	33.5	37.2	30.9	26.6	10.1	10.8	73.6	71.0	72.8	68.9	47.1	25.8	25.4
2h	52.6	53.2	32.1	31.2	34.5	15.5	21.8	78.5	52.0	55.6	37.9	38.0	14.0	23.1
2i	73.7	69.6	61.6	62.3	46.3	40.4	38.5	67.2	66.9	57.6	47.5	29.5	28.9	21.9
2j	18.8	8.8	9.4	7.9	6.3	6.6	7.9	41.8	33.1	27.6	22.4	16.5	14.0	14.8
敌草隆Diuron	35.2	27.3	26.3	20.8	24.9	14.0	12.3	100.0	97.0	95.4	95.9	95.7	89.9	53.1

化合物 compound	茎stem			根root
化合物 compound	方程equations	R	IC₅₀/(mmol·L^-1)	方程equations	R	IC₅₀/(mmol·L^-1)
1	y=5.2933+1.9813x	0.9302	0.71	y=6.3625+2.4477x	0.9115	0.28
2f	y=5.8331+1.8630x	0.9803	0.36	y=6.4629+1.9043x	0.9853	0.17
2g	y=4.4583+0.5900x	0.9054	>5	y=5.2972+0.8263x	0.9158	0.44
2h	y=4.6838+0.5526x	0.8911	3.73	y=4.9693+0.8639x	0.9191	1.09
2i	y=5.2743+0.5551x	0.9753	0.32	y=5.0318+0.7570x	0.9761	0.91
敌草隆Diuron	y=4.3166+0.3951x	0.9330	>5	y=7.2970+1.8912x	0.8224	0.06

化合物 compound	抑制率inhibition rate(10 μmol/L)/%
化合物 compound	HUVEC-C	BALB/C 3T3
1	0.95	0.75
2a	0.59	0.33
2b	0.12	1.25
2c	2.49	-0.17
2d	7.23	-0.50
2e	0.12	0.92
2f	1.30	0.84
2g	-0.36	1.09
2h	0.47	0.84
2i	2.13	1.17
2j	2.73	4.59

[1]	侯文彪, 江文夺, 吴嘉超, 梁杰珍, 王琳琳, 陈小鹏. 松脂气液平衡特性及其N₂/CO₂循环活气法蒸馏过程分析[J]. 林产化学与工业, 2021, 41(5): 93-99.
[2]	董阜豪, 周新成, 孙鹏昊, 郭丽珍, 徐徐, 王石发. 松节油基聚酰胺阻燃材料的制备与表征[J]. 林产化学与工业, 2021, 41(1): 21-28.
[3]	何云,段文贵,林桂汕,岑波,卜俊文,雷福厚. 柠檬醛基缩氨基硫脲化合物的合成及除草活性[J]. 林产化学与工业, 2020, 40(3): 76-84.
[4]	曾小静,徐士超,王婧,董欢欢,陈玉湘,赵振东. 紫苏醇酯的合成及除草活性研究[J]. 林产化学与工业, 2019, 39(6): 53-58.
[5]	郑万里, 马献力, 周小群, 李芳耀, 辛懋, 蒋彩娜. 樟脑酸基酰腙类化合物的合成及其抑菌、除草活性研究[J]. 林产化学与工业, 2019, 39(5): 41-49.
[6]	徐士超,曾小静,董欢欢,赵振东. 萜类植物源除草活性物开发及应用研究进展[J]. 林产化学与工业, 2019, 39(2): 1-8.
[7]	马晓江,王进,汤锋,高全,刘伟,宋丽. 无患子总皂苷减压提取工艺优化及其除草活性研究[J]. 林产化学与工业, 2019, 39(1): 108-114.
[8]	马媛, 段文贵, 林桂汕, 刘陆智, 黄正松, 雷福厚. 紫苏醛基席夫碱-(硫)脲化合物的合成及生物活性[J]. 林产化学与工业, 2017, 37(1): 54-62.
[9]	王红琴, 王亚明, 蒋丽红, 晋艳琼. [Rh(COD)Cl]₂催化剂的制备及催化松节油加氢反应[J]. 林产化学与工业, 2016, 36(6): 56-62.
[10]	王朋娜, 徐徐, 蔡涛, 黄建峰, 王石发. 异长叶烷酮与水合肼的合成反应[J]. 林产化学与工业, 2016, 36(2): 129-133.
[11]	韩欢, 蒋丽红, 王亚明, 黄太阳, 王红琴. Ni/TiO₂-Al₂O₃催化剂的制备及其在松节油催化加氢反应中的应用[J]. 林产化学与工业, 2016, 36(1): 92-98.
[12]	廖圣良, 商士斌, 司红燕, 沈明贵, 饶小平, 宋湛谦. 羧酸桃金娘烷醇酯的合成及抑菌活性研究[J]. 林产化学与工业, 2015, 35(6): 33-38.
[13]	彭晗, 杨丽娟, 徐徐, 王石发. 异长叶烯酮的绿色合成研究[J]. 林产化学与工业, 2015, 35(3): 97-103.
[14]	王婧;赵振东;毕良武;李冬梅;. 松节油中主要单萜烯的异构方法综述[J]. 林产化学与工业, 2013, 33(2): 144-150.
[15]	段文贵;李行任;马献力;莫启进;许雪棠;岑波. 5-去氢枞基-1,3,4-噻二唑衍生物的合成和除草活性[J]. 林产化学与工业, 2011, 31(1): 1-8.

3-对烯-1-磺酰胺类化合物的合成及其除草活性

Synthesis and Herbicidal Activity Investigation of p-Menth-3-en-1-sulfonamide Compounds

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 4

参考文献 15

相关文章 15

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们