硫酸肼

硫酸肼
	IUPAC名; Hydrazinium hydrogen sulfate
别名	硫酸联氨; 硫酸氢肼
识别
CAS号	10034-93-2
PubChem	24842
ChemSpider	23225
SMILES	O=S(=O)(O)O.NN;
InChI	1/H4N2.H2O4S/c1-2;1-5(2,3)4/h1-2H2;(H2,1,2,3,4);
InChIKey	ZGCHATBSUIJLRL-UHFFFAOYAL
EINECS	233-110-4
性质
化学式	N2H4·H2SO4
外观	无色结晶
熔点	254 °C
沸点	分解
溶解性（水）	30 g/L (20 °C)
危险性
警示术语	R：R23/24/25-R34-R43-R45-R50-R53
安全术语	S：S45-S53-S60-S61
MSDS	External MSDS
欧盟编号	007-008-00-3
欧盟分类	T N C
	致死量或浓度：
LD50（中位剂量）	601 mg/kg (大鼠经口)
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

硫酸肼^[2]是联氨与硫酸生成的盐类，指N₂H₅HSO₄和N₂H₆SO₄两种物质，常写作N₂H₄·H₂SO₄。

N₂H₆SO₄遇水完全水解，产生N₂H₅HSO₄，而N₂H₅HSO₄尚未分离得到固体。^[3]N₂H₆SO₄固体在室温下可以以正交晶系或单斜晶系存在。^[4]

性质[编辑]

无色无味鳞状结晶或斜方结晶。微溶于冷水，易溶于热水，水溶液呈酸性。不溶于醇。在空气中稳定，不易吸湿。为强还原剂。不可与碱类、氧化剂共存。有毒，致癌。^[5]^[6]

硫酸肼受热分解，其分解产物是硫酸铵和硫酸氢铵。^[3]

制备[编辑]

尿素、次氯酸钠、液碱在高锰酸钾存在下反应，制得肼，经蒸馏，再同硫酸发生中和，生成物经冷却结晶、过滤、干燥，制得硫酸肼成品。

{\rm {\ NaOCl+NH_{2}CONH_{2}+2NaOH{\xrightarrow {KMnO_{4}}}N_{2}H_{4}\cdot H_{2}O+}}

{\rm {\ NaCl+Na_{2}CO_{3}}}

{\rm {\ N_{2}H_{4}\cdot H_{2}O+H_{2}SO_{4}\rightarrow N_{2}H_{4}\cdot H_{2}SO_{4}+H_{2}O}}

硫酸氢铵和水合肼反应，也能得到硫酸肼：^[3]

NH₄HSO₄ + N₂H₄·H₂O → N₂H₅HSO₄ + NH₃ + H₂O

用途[编辑]

用作有机合成试剂，用于制取偶氮二异丁腈，以及制造药品、杀虫剂、灭菌剂等。化学镀时用作还原剂。也用作塑料和橡胶的发泡剂等。

硫酸肼在美国是营养补充剂，用以对抗癌症造成的患者厌食、消瘦等症状。^[7]^[8]^[9]^[10] 1970年代中期美国的 Joseph Gold^[11]^[12] 首先提出硫酸肼治疗法以控制癌患者恶病质的发展。其原理是癌细胞需要靠葡萄糖的糖酵解来产生能量，而此过程的产物乳酸在肝脏中又经过另一耗能过程——糖异生再转变为葡萄糖。由于肼是化学性质很活泼的化合物，可能在体内对糖异生中的磷酸烯醇式丙酮酸羧化激酶有抑制作用，因此使用硫酸肼可能阻断糖异生过程，并因此控制恶病质的发展。^[13] 这一替代医学疗法在1990年代中期因《阁楼》成人杂志创办人妻子 Kathy Keeton 的宣传而广为人知。Keeton 曾用这一方法治疗自己的转移性乳腺癌，^[14] 并声称自己因使用这一疗法而使寿命延长数年。不过至今，硫酸肼疗法的效果仍然受到很大的争议。

参考资料[编辑]

^ ^1.0 ^1.1 ^1.2 Safety (MSDS) data for hydrazine sulfate
^ 硫酸肼（Hydrazine sulfate）物質安全資料表 (PDF). 國立高雄應用科技大學化工系. [2017-08-14]. （原始内容 (PDF)存档于2017-08-14）.
^ ^3.0 ^3.1 ^3.2 K. C. Patil. Inorganic Hydrazine Derivatives - Synthesis, Properties and Applications. Wiley, 2014
^ K.C. PATIL, J.P. VITTAL. DSC STUDIES ON THE PHASE TRANSFORMATION OF HYDRAZONIUM SULFATE. Materials Chemistry. 1982. (7): 577-586
^ Hydrazine Hazard Summary, U.S. Environmental Protection Agency, January 2000 [2009-11-24], （原始内容存档于2009-09-27） .
^ Section 9.2.1, Environmental Health Criteria for Hydrazine, International Programme on Chemical Safety, 1987 [2009-11-24], （原始内容存档于2010-03-14） .
^ Chlebowski, R. T.; Bulcavage, L.; Grosvenor, M.; et al, Hydrazine Sulfate in Cancer Patients With Weight Loss. A Placebo-Controlled Clinical Experience, Cancer, 1987, 59 (3): 406–10 [2009-11-24], PMID 3791153, （原始内容存档于2014-11-30） .
^ Brauer, M.; Inculet, R. I.; Bratnager, G.; Marsh, G. D.; Driedger, A. A.; Thompson, R. T., Insulin Protects against Hepatic Bioenergetic Deterioration by Cancer Cachexia. An in-Vivo ³¹P Magnetic Resonance Study, Cancer Research, 1994, 54 (24): 6383–86 [2009-11-24], PMID 7987832, （原始内容存档于2008-08-21） .
^ Chlebowski, R. T.; Bulcavage, L.; Grosvenor, M.; Oktay, E.; Block, J. B.; Chlebowski, J. S.; Ali, I.; Elashoff, R., Hydrazine Sulfate Influence on Nutritional Status and Survival in Non-Small-Cell Lung Cancer, Journal of Clinical Oncology, 1990, (8): 9–15 [2009-11-24], PMID 1688616, （原始内容存档于2014-09-28） .
^ Gold, J., Long term complete response in patient with advanced, localized NSCLC with hydrazine sulfate, radiation and Carboplatin, refractory to combination chemotherapy, Proceedings of the American Association for Cancer Research, 1999, (40): 642 . Abstract. （页面存档备份，存于互联网档案馆）
^ Kaegi, Elizabeth, Unconventional therapies for cancer: 4. Hydrazine sulfate. Task Force on Alternative Therapies of the Canadian Breast Cancer Research Initiative, Canadian Medical Association Journal, 1998, 158 (10): 1327–30, PMID 9614826 .
^ Gold J. Hydrazine sulfate: a current perspective. Nutr Cancer. 1987, 9 (2-3): 59–66. PMID 3104888.
^ Gold, J., Proposed Treatment of Cancer by Inhibition of Gluconeogenesis, Oncology, 1968, 22 (2): 185–207, PMID 5688432 .
^ London, William M., Penthouse's promotion of hydrazine sulfate, July 23, 2006 [2009-11-24], （原始内容存档于2009-08-17）

[ox-1] 1.0 ^1.1 ^1.2 Safety (MSDS) data for hydrazine sulfate

[2] 硫酸肼（Hydrazine sulfate）物質安全資料表 (PDF). 國立高雄應用科技大學化工系. [2017-08-14]. （原始内容 (PDF)存档于2017-08-14）.

[hydrazine-3] 3.0 ^3.1 ^3.2 K. C. Patil. Inorganic Hydrazine Derivatives - Synthesis, Properties and Applications. Wiley, 2014

[4] K.C. PATIL, J.P. VITTAL. DSC STUDIES ON THE PHASE TRANSFORMATION OF HYDRAZONIUM SULFATE. Materials Chemistry. 1982. (7): 577-586

[EPA-5] Hydrazine Hazard Summary, U.S. Environmental Protection Agency, January 2000 [2009-11-24], （原始内容存档于2009-09-27） .

[EHC-6] Section 9.2.1, Environmental Health Criteria for Hydrazine, International Programme on Chemical Safety, 1987 [2009-11-24], （原始内容存档于2010-03-14） .

[7] Chlebowski, R. T.; Bulcavage, L.; Grosvenor, M.; et al, Hydrazine Sulfate in Cancer Patients With Weight Loss. A Placebo-Controlled Clinical Experience, Cancer, 1987, 59 (3): 406–10 [2009-11-24], PMID 3791153, （原始内容存档于2014-11-30） .

[8] Brauer, M.; Inculet, R. I.; Bratnager, G.; Marsh, G. D.; Driedger, A. A.; Thompson, R. T., Insulin Protects against Hepatic Bioenergetic Deterioration by Cancer Cachexia. An in-Vivo ³¹P Magnetic Resonance Study, Cancer Research, 1994, 54 (24): 6383–86 [2009-11-24], PMID 7987832, （原始内容存档于2008-08-21） .

[9] Chlebowski, R. T.; Bulcavage, L.; Grosvenor, M.; Oktay, E.; Block, J. B.; Chlebowski, J. S.; Ali, I.; Elashoff, R., Hydrazine Sulfate Influence on Nutritional Status and Survival in Non-Small-Cell Lung Cancer, Journal of Clinical Oncology, 1990, (8): 9–15 [2009-11-24], PMID 1688616, （原始内容存档于2014-09-28） .

[10] Gold, J., Long term complete response in patient with advanced, localized NSCLC with hydrazine sulfate, radiation and Carboplatin, refractory to combination chemotherapy, Proceedings of the American Association for Cancer Research, 1999, (40): 642 . Abstract. （页面存档备份，存于互联网档案馆）

[Kaegi-11] Kaegi, Elizabeth, Unconventional therapies for cancer: 4. Hydrazine sulfate. Task Force on Alternative Therapies of the Canadian Breast Cancer Research Initiative, Canadian Medical Association Journal, 1998, 158 (10): 1327–30, PMID 9614826 .

[12] Gold J. Hydrazine sulfate: a current perspective. Nutr Cancer. 1987, 9 (2-3): 59–66. PMID 3104888.

[13] Gold, J., Proposed Treatment of Cancer by Inhibition of Gluconeogenesis, Oncology, 1968, 22 (2): 185–207, PMID 5688432 .

[14] London, William M., Penthouse's promotion of hydrazine sulfate, July 23, 2006 [2009-11-24], （原始内容存档于2009-08-17）

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