双头季铵盐和噻二唑衍生物的合成及性能研究
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摘要
本文通过二甲基十二烷基叔胺与卤代烃的取代反应合成了六种双头季铵盐
表面活性剂。它们分别是溴化 N,N,N’,N’-四甲基-N,N’-双十二烷基-1,2-苯二亚甲
基二铵(1,2-DBnQA)、溴化 N,N,N’,N’-四甲基-N,N’-双十二烷基-1,3-苯二亚甲基二
铵(1,3-DBnQA)、溴化 N,N,N’,N’-四甲基-N,N’-双十二烷基-1,4-苯二亚甲基二铵
(1,4-DBnQA)、溴化 N,N,N’,N’-四甲基-N,N’-双十二烷基-1,4-丁铵(1,4-DBuQA)、
溴化 N,N,N’,N’-四甲基-N,N’-双十二烷基-2-丁烯-1,4-二铵(1,4-DBeQA)和溴化
N,N,N’,N’-四甲基-N,N’-双十二烷基-2-丁炔-1,4-二铵(1,4-DByQA)。其中，后两种
化合物未见文献报道。利用红外光谱、核磁共振氢谱对这六种物质的结构进行了
表征。并通过微生物实验方法对上述物质的杀菌活性进行了测试。结果表明双季
铵盐类化合物的杀菌性能明显高于单季铵盐类化合物，且在双头季铵盐中连接基
团为芳基时杀菌活性要高于连接基团为脂肪族类的季铵盐，同时烃类连接基团的
不饱和程度提高也会增加其杀菌活性。
本文还用 2,5-二巯基-1,3,4-噻二唑与卤代物反应合成了六种噻二唑衍生物。
它们分别是 2,5-二甲硫基-1,3,4-噻二唑(DMTZ)、2,5-二乙硫基-1,3,4-噻二唑
(DETZ)、2,5-二苄硫基-1,3,4-噻二唑(DBTZ)、1,4-双(5-巯基-1,3,4-噻二唑-2-硫
基)-2-丁烯(BeTZ)、4,16-二氧-1,7,13,19-四硫[7.7]-(2,5)-1,3,4-噻二唑(DATZ)和笼状
噻二唑衍生物(TBTZ)。其中 BeTZ 和 TBTZ 未见报道。利用红外光谱、核磁共振
氢 谱 和 元 素 分 析 对 六 种 化 合 物 的 结 构 进 行 了 表 征 。 得 到 DATZ 和
{[Ag2(DMTZ)4](ClO4)2}∞的单晶体，用红外光谱和 X-射线单晶衍射法对结构进行
了鉴定。在{[Ag2(DMTZ)4](ClO4)2}∞中 Ag 有两种配位方式，其中一种是与四个
属于不同噻二唑环上的 N 原子配位，另一种是与属于不同噻二唑环上的三个 N
和一个 S 原子配位。
Six compounds of bis(quaternary ammonium), 1,2-bis(N,N-dimethyl-N-dodecyl
ammonium bromide-N-methylene) benzene (1,2-DBnQA), 1,3-bis(N,N-dimethyl-N-
dodecyl ammonium bromide-N-methylene) benzene (1,3-DBnQA),
1,4-bis(N,N-dimethyl-N-dodecyl ammonium bromide-N-methylene)benzene
(1,4-DBnQA), 1,4-bis(N,N-dimethyl-N-dodecyl ammonium bromide)butane
(1,4-DBuQA), 1,4-bis(N,N-dimethyl-N-dodecyl ammonium bromide)-2-butylene
(1,4-DBeQA) and 1,4-bis(N,N-dimethyl-N-dodecyl ammonium bromide)-2-butyne
(1,4-DByQA) were synthesized by the reaction between dimethyldodecylamine and
varied dibromides. The latter two are new compounds. All of them have been
determined by IR and H NMR. The bioactivities of these quaternary ammonium
1
Gemini surfactants have been determined. They all have the higher antibacterial
properties than the mono(quaternary ammonium). We also find that the bioactivities
increase with the decrease of the saturation of the linkers.
The compounds of 2,5-dimercapto-1,3,4-thiadiazole derivatives,
2,5-bis(methylthio)-1,3,4-thiadizole (DMTZ), 2,5-bis(ethylthio)-1,3,4-thiadizole
(DETZ), 2,5-bis(benzylthio)-1,3,4-thiadizole (DBTZ), 1,4-bis(5-mercapto-1,3,4-
thiadizole-2-thio)-2-butene (BeTZ), 4,16- dioxa-1,7,13,19-tetrathia[7.7]-(2,5)-1,3,4-
thiadiazolophane (DATZ), cagelike thiadiazole derivative (TBTZ) were synthesized
by the reaction between 2,5-dimercapto-1,3,4-thiadiazole and varied halides. BeTZ
and TBTZ are new compounds. The structures of them have been determined by IR,
1H NMR and element analysis. The crystal structure of {[Ag2(DMTZ)4](ClO4)2}∞ was
determined by IR and X-ray diffraction. It was found that the Ag ions coordinate with
S and N from different thiadiazole.
表面活性剂。它们分别是溴化 N,N,N’,N’-四甲基-N,N’-双十二烷基-1,2-苯二亚甲
基二铵(1,2-DBnQA)、溴化 N,N,N’,N’-四甲基-N,N’-双十二烷基-1,3-苯二亚甲基二
铵(1,3-DBnQA)、溴化 N,N,N’,N’-四甲基-N,N’-双十二烷基-1,4-苯二亚甲基二铵
(1,4-DBnQA)、溴化 N,N,N’,N’-四甲基-N,N’-双十二烷基-1,4-丁铵(1,4-DBuQA)、
溴化 N,N,N’,N’-四甲基-N,N’-双十二烷基-2-丁烯-1,4-二铵(1,4-DBeQA)和溴化
N,N,N’,N’-四甲基-N,N’-双十二烷基-2-丁炔-1,4-二铵(1,4-DByQA)。其中，后两种
化合物未见文献报道。利用红外光谱、核磁共振氢谱对这六种物质的结构进行了
表征。并通过微生物实验方法对上述物质的杀菌活性进行了测试。结果表明双季
铵盐类化合物的杀菌性能明显高于单季铵盐类化合物，且在双头季铵盐中连接基
团为芳基时杀菌活性要高于连接基团为脂肪族类的季铵盐，同时烃类连接基团的
不饱和程度提高也会增加其杀菌活性。
本文还用 2,5-二巯基-1,3,4-噻二唑与卤代物反应合成了六种噻二唑衍生物。
它们分别是 2,5-二甲硫基-1,3,4-噻二唑(DMTZ)、2,5-二乙硫基-1,3,4-噻二唑
(DETZ)、2,5-二苄硫基-1,3,4-噻二唑(DBTZ)、1,4-双(5-巯基-1,3,4-噻二唑-2-硫
基)-2-丁烯(BeTZ)、4,16-二氧-1,7,13,19-四硫[7.7]-(2,5)-1,3,4-噻二唑(DATZ)和笼状
噻二唑衍生物(TBTZ)。其中 BeTZ 和 TBTZ 未见报道。利用红外光谱、核磁共振
氢 谱 和 元 素 分 析 对 六 种 化 合 物 的 结 构 进 行 了 表 征 。 得 到 DATZ 和
{[Ag2(DMTZ)4](ClO4)2}∞的单晶体，用红外光谱和 X-射线单晶衍射法对结构进行
了鉴定。在{[Ag2(DMTZ)4](ClO4)2}∞中 Ag 有两种配位方式，其中一种是与四个
属于不同噻二唑环上的 N 原子配位，另一种是与属于不同噻二唑环上的三个 N
和一个 S 原子配位。
Six compounds of bis(quaternary ammonium), 1,2-bis(N,N-dimethyl-N-dodecyl
ammonium bromide-N-methylene) benzene (1,2-DBnQA), 1,3-bis(N,N-dimethyl-N-
dodecyl ammonium bromide-N-methylene) benzene (1,3-DBnQA),
1,4-bis(N,N-dimethyl-N-dodecyl ammonium bromide-N-methylene)benzene
(1,4-DBnQA), 1,4-bis(N,N-dimethyl-N-dodecyl ammonium bromide)butane
(1,4-DBuQA), 1,4-bis(N,N-dimethyl-N-dodecyl ammonium bromide)-2-butylene
(1,4-DBeQA) and 1,4-bis(N,N-dimethyl-N-dodecyl ammonium bromide)-2-butyne
(1,4-DByQA) were synthesized by the reaction between dimethyldodecylamine and
varied dibromides. The latter two are new compounds. All of them have been
determined by IR and H NMR. The bioactivities of these quaternary ammonium
1
Gemini surfactants have been determined. They all have the higher antibacterial
properties than the mono(quaternary ammonium). We also find that the bioactivities
increase with the decrease of the saturation of the linkers.
The compounds of 2,5-dimercapto-1,3,4-thiadiazole derivatives,
2,5-bis(methylthio)-1,3,4-thiadizole (DMTZ), 2,5-bis(ethylthio)-1,3,4-thiadizole
(DETZ), 2,5-bis(benzylthio)-1,3,4-thiadizole (DBTZ), 1,4-bis(5-mercapto-1,3,4-
thiadizole-2-thio)-2-butene (BeTZ), 4,16- dioxa-1,7,13,19-tetrathia[7.7]-(2,5)-1,3,4-
thiadiazolophane (DATZ), cagelike thiadiazole derivative (TBTZ) were synthesized
by the reaction between 2,5-dimercapto-1,3,4-thiadiazole and varied halides. BeTZ
and TBTZ are new compounds. The structures of them have been determined by IR,
1H NMR and element analysis. The crystal structure of {[Ag2(DMTZ)4](ClO4)2}∞ was
determined by IR and X-ray diffraction. It was found that the Ag ions coordinate with
S and N from different thiadiazole.
引文
[1] Singh, N. K., Synthetic: structure and antifungal srudies of some 3d-metal
complexes of salicylaldehyde-2-furanthiocarboxyhydrazone, Syhth React Inorg
Met-Org Chem, 1985, 15: 75
[2] Gingras, B. A., Hormal, R. W. and Bayley, C. H., The preparation of some
46
天津大学硕士学位论文
thiosemicarbazone and their copper complexes, Can. J. Chem., 1960, 38: 712
[3] Dobek, A. S., Klayman, D. L., Scovil, J. P., et al, Antibacterial properities of
2-acetylpyridine-1-oxide thiosemicarbazones, Chemotherapy, 1986, 32: 25
[4] 王锐，颐旭初，靳立人等，噻吩酮、醛缩氨基硫脲衍生物的合成，中国药物
大学学报，1990，21(1): 6
[5] Japan Patent, 07,338,146, Jul.25, 1995
[6] Schuster, G. J. H. & Schwarz, J. Z., Pflanzenkrankh Pflanzen Scutz, 1994, 91(6):
569-579
[7] Gupta, A. S. et al., J. Indian Chem. Soc., 1988, 65(3): 225-226
[8] Lester A. Doe, Jr., Surface coating compositions containing substituted
1,3,4-Thiadiazoles, United States Patent, 4711915, Dec. 8, 1987
[9] Dvoracek L. M., Antifoulant additives for high temperature hydrocarbon
processing, United States Patent, 4719001, Jan.12, 1988
[10] Fabretti A. C., Franchinal G. C. and Peyronel G., Cobalt(II), Nickel(II), Copper(II)
and Copper(I) Complexes of 2-Mercapto-5-methyl-1,3,4-thiadiazole and
2,5-Bis(methylmercapto)-1,3,4-thiadiazole, Transition Met. Chem., 1982, 7:
105-108
[11] Raper, E. S., Copper complex with thiadiazole, Coord. Chem. Rev., 1994,
129(1-2): 91-156
[12] Pappalardo S., Bottino F. and Tringali C., Synthesis and Structural Aspects of
(2,5)-1,3,4-Thiadiazolino Thia Crown Ethers, J. Org. Chem., 1987, 52: 3409-3413
[13] Pappalardo S. & Occhipinti S., Mass Spectrometry of 1,3,4-Thiadiazolo
Thiacrown Ethers, Organic Mass Spectrometry, 1987, 22: 269-278
[14] Fabretti, A. C., Franchini, G. C. and Peyronel, G., Spectrochim. Acta, (Part A),
1980, 36: 517-520
[15] J. Závada, M. Pánková, P. Holy, et al., A facile synthesis of
Hwxakis(bromomethyl)benzene from mesityene, Synthesis, 1994, 1132
[16 ] Mahmoud Al-Talib & Hasan Tashtoush, Unususl rearrangement in reactions of
propanodihydrazide and butanodihydrazide with carbon disulfide, India Journal of
Chemisrry, 1999, 38B: 1374-1376
[17] Pappalardo, S., Bottino, F. and Tringali, C., Chemistry of N-Heterocyclic Sulfur
Compounds, J. Org. Chem., 1987, 52: 405-412
[18] Chande M. S. & Athalye S. S., Chemistry of N-Heterocyclic Sulphur compounds:
Part II: Regioselective Synthesis of N,N’-diaminotriazolophanes Containing
Oxygen and Sulphur Heteroatoms, Synthetic Communications, 2000, 30(9):
1667-1674
[19] Yang, C., Chen, X. M. and Lu, X. Q., First metal-encapsulating star
48
天津大学硕士学位论文
polysulfoxide incorporating 2-amino-1,3,4-thiadiazole, Chem. Commun., 1997,
2041-2042
[20] Zheng, Y., Du, M. and Li, J. R., Tuning the framework formation of silver(I)
corrdination architectures with heterocyclic thioerhers, Dalton Trans., 2003,
1509-1514
[21] Raper, E. S., Copper complexs of heterocyclic thioamides and related ligands,
Coord. Chem. Rev., 1994, 129: 91-156
[22] Zhang, W., Liu, H. M., Li, Ch. B. & Zhang, W. Q.,2,2’-[1,4-phenylenebis
(methylenethio)]bisthiazole, Acta Cryst, 2003, E59: o1-o2
complexes of salicylaldehyde-2-furanthiocarboxyhydrazone, Syhth React Inorg
Met-Org Chem, 1985, 15: 75
[2] Gingras, B. A., Hormal, R. W. and Bayley, C. H., The preparation of some
46
天津大学硕士学位论文
thiosemicarbazone and their copper complexes, Can. J. Chem., 1960, 38: 712
[3] Dobek, A. S., Klayman, D. L., Scovil, J. P., et al, Antibacterial properities of
2-acetylpyridine-1-oxide thiosemicarbazones, Chemotherapy, 1986, 32: 25
[4] 王锐，颐旭初，靳立人等，噻吩酮、醛缩氨基硫脲衍生物的合成，中国药物
大学学报，1990，21(1): 6
[5] Japan Patent, 07,338,146, Jul.25, 1995
[6] Schuster, G. J. H. & Schwarz, J. Z., Pflanzenkrankh Pflanzen Scutz, 1994, 91(6):
569-579
[7] Gupta, A. S. et al., J. Indian Chem. Soc., 1988, 65(3): 225-226
[8] Lester A. Doe, Jr., Surface coating compositions containing substituted
1,3,4-Thiadiazoles, United States Patent, 4711915, Dec. 8, 1987
[9] Dvoracek L. M., Antifoulant additives for high temperature hydrocarbon
processing, United States Patent, 4719001, Jan.12, 1988
[10] Fabretti A. C., Franchinal G. C. and Peyronel G., Cobalt(II), Nickel(II), Copper(II)
and Copper(I) Complexes of 2-Mercapto-5-methyl-1,3,4-thiadiazole and
2,5-Bis(methylmercapto)-1,3,4-thiadiazole, Transition Met. Chem., 1982, 7:
105-108
[11] Raper, E. S., Copper complex with thiadiazole, Coord. Chem. Rev., 1994,
129(1-2): 91-156
[12] Pappalardo S., Bottino F. and Tringali C., Synthesis and Structural Aspects of
(2,5)-1,3,4-Thiadiazolino Thia Crown Ethers, J. Org. Chem., 1987, 52: 3409-3413
[13] Pappalardo S. & Occhipinti S., Mass Spectrometry of 1,3,4-Thiadiazolo
Thiacrown Ethers, Organic Mass Spectrometry, 1987, 22: 269-278
[14] Fabretti, A. C., Franchini, G. C. and Peyronel, G., Spectrochim. Acta, (Part A),
1980, 36: 517-520
[15] J. Závada, M. Pánková, P. Holy, et al., A facile synthesis of
Hwxakis(bromomethyl)benzene from mesityene, Synthesis, 1994, 1132
[16 ] Mahmoud Al-Talib & Hasan Tashtoush, Unususl rearrangement in reactions of
propanodihydrazide and butanodihydrazide with carbon disulfide, India Journal of
Chemisrry, 1999, 38B: 1374-1376
[17] Pappalardo, S., Bottino, F. and Tringali, C., Chemistry of N-Heterocyclic Sulfur
Compounds, J. Org. Chem., 1987, 52: 405-412
[18] Chande M. S. & Athalye S. S., Chemistry of N-Heterocyclic Sulphur compounds:
Part II: Regioselective Synthesis of N,N’-diaminotriazolophanes Containing
Oxygen and Sulphur Heteroatoms, Synthetic Communications, 2000, 30(9):
1667-1674
[19] Yang, C., Chen, X. M. and Lu, X. Q., First metal-encapsulating star
48
天津大学硕士学位论文
polysulfoxide incorporating 2-amino-1,3,4-thiadiazole, Chem. Commun., 1997,
2041-2042
[20] Zheng, Y., Du, M. and Li, J. R., Tuning the framework formation of silver(I)
corrdination architectures with heterocyclic thioerhers, Dalton Trans., 2003,
1509-1514
[21] Raper, E. S., Copper complexs of heterocyclic thioamides and related ligands,
Coord. Chem. Rev., 1994, 129: 91-156
[22] Zhang, W., Liu, H. M., Li, Ch. B. & Zhang, W. Q.,2,2’-[1,4-phenylenebis
(methylenethio)]bisthiazole, Acta Cryst, 2003, E59: o1-o2