玫棕酸

玫棕酸
	IUPAC名; 5,6-Dihydroxycyclohex-5-ene-1,2,3,4-tetrone; 5,6-二羟基-5-环己烯-1,2,3,4-四酮
别名	二羟基二喹啉; 二氧二醌; 玫瑰红酸
识别
CAS号	118-76-3（二水合物）
PubChem	67050
ChemSpider	60401
SMILES	C1(=C(C(=O)C(=O)C(=O)C1=O)O)O;
InChI	1/C6H2O6/c7-1-2(8)4(10)6(12)5(11)3(1)9/h7-8H;
InChIKey	WCJLIWFWHPOTAC-UHFFFAOYAV
EINECS	204-276-5
MeSH	C005690
性质
化学式	C6H2O6
熔点	130 - 132 °C（271 K）
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

玫棕酸（英语：Rhodizonic acid）是化学式为C
6H
2O
6或(CO)
4(COH)
2的化合物。它可以看作是环己烯的二重烯醇和四重酮。

Quick Facts 玫棕酸, 识别 ...

Close

玫棕酸通常以二水合物C
6H
2O
6 · 2H₂O的形式获得。后者实际上是2,3,5,5,6,6-六羟基-2-环己烯-1,4-二酮，其中两个原始酮基团被两对偕二醇取代。二水合物经低压升华可得橙色至深红色、吸湿性强的无水酸。^[1]^[2]

与许多其他烯醇一样，玫棕酸可以从羟基中失去氢正离子H⁺（pK_a1 = 7000437800000000000♠4.378±0.009, pK_a2 = 7000465200000000000♠4.652±0.014 at 25 °C）^[3]，产生玫棕酸氢根阴离子C
6HO−
6和玫棕酸根阴离子C
6O2−
6。后者芳香族和对称，因为双键的离域电子均匀分布在六个CO单元上。玫棕酸盐往往具有各种深浅不一的红色，从淡黄色到紫色。

玫棕酸已用于钡、铅和其他金属的化学分析。^[4]特别是玫棕酸钠测试可用于检测受试者手中的枪击残留物（其中含铅）^[5]，并区分箭伤和枪伤以执行狩猎法规。^[6]

1837年，奥地利化学家约翰·海勒通过分析加热碳酸钾和木炭混合物的产物发现了玫棕酸。 ^[7]^[8]^[9]这个名字来自希腊语ῥοδίζω（rhodizō，“染红”）^[10]，由于其盐的颜色。

盐

玫棕酸盐在透射光中往往具有各种深浅的红色，从淡黄色到紫色，在反射光中具有绿色光泽。

可以通过用硝酸氧化肌醇并在氧气的存在下与乙酸钾反应制备玫棕酸钾。由于其在水中的相对难溶性，玫棕酸盐可从溶液中结晶。^[11]

玫棕酸钠呈深棕色，在干燥时稳定^[12]，但水溶液会在几天内分解，即使在冰箱中也是如此。^[4]玫棕酸铅是深紫色的。^[12]^[13]

氧化和分解

玫棕酸是氧化产物链的成员：苯六酚（(COH)
6）、四羟基对苯醌（THBQ）（(COH)
4(CO)
2）、玫棕酸（(COH)
2(CO)
4）和环己六酮（(CO)
6）。^[4]已考虑将玫棕酸锂与THBQ 盐和苯六酚一起用于可充电电池中。^[14]一价阴离子C
6O−
6已在质谱实验中检测到。^[15]

玫棕酸和玫棕酸根阴离子可以失去一个CO单元以产生克酮酸（(CO)
3(COH)
2）和克酮酸根阴离子（C
5O2−
5），其机制仍然未完全了解。在碱性溶液（pH>10）中，玫棕酸在没有氧气的条件下迅速转化为THBQ阴离子（(CO)4−
6）而在有氧气的情况下则转化为克酮酸。在pH=8.3和光照条件下，溶液在没有氧气的情况下可以稳定数天，在有氧气的情况下分解成克酮酸和其他产物（可能包括环己六酮或十二羟基环己烷）。^[16]^[17]

酸

在溶液中，玫棕酸和玫棕酸氢根离子大部分是水合的，一些羰基>C=O被偕羟基>C(OH)
2取代。^[3]

盐

在无水玫棕酸铷（Rb
2C
6O
6）中，玫棕酸阴离子以平行柱状堆积，铷离子也是如此。在垂直于柱的平面中，它们排列成两个交错的六边形网格。阴离子是平面的。^[2]

无水玫棕酸钾（K
2C
6O
6）具有独特但相似的结构。阴离子和阳离子排列在交替的平面上。在每个平面内，阴离子排列成六边形网格。每个钾离子的排列方式使其对称地连接到四个阴离子上的八个氧，每个相邻平面有两个。阴离子略微扭曲成船形（与平均平面的rms偏差为0.108Å）。^[18]玫棕酸钠（Na
2C
6O
6）具有相同的结构，但阴离子稍有扭曲（rms为0.113Å）^[19]

在溶液中，玫棕酸根阴离子不会水合。^[3]

乙炔二醇 (COH)
2
三角酸 (CO)(COH)
2
方酸 (CO)
2(COH)
2
巴豆酸 (CO)
3(COH)
2

[1]
Patton, E.; West, R. New aromatic anions. VIII. Acidity constants of rhodizonic acid. Journal of Physical Chemistry. 1970, 74 (12): 2512–2518. doi:10.1021/j100706a018.
[2]
Braga, D.; Cojazzi, G.; Maini, L.; Grepioni, F. Reversible solid-state interconversion of rhodizonic acid H₂C₆O₆ into H₆C₆O₈ and the solid-state structure of the rhodizonate dianion C
6O2−
6 (aromatic or non-aromatic?). New Journal of Chemistry. 2001, 25: 1221−1223. doi:10.1039/b107317f.
[3]
Gelb, R. I.; Schwartz, L. M.; Laufer, D. A. The structure of aqueous rhodizonic acid. Journal of Physical Chemistry. 1978, 82 (18): 1985–1988. doi:10.1021/j100507a006.
[4]
Chalmers, R. A.; Telling, G. M. A reassessment of rhodizonic acid as a qualitative reagent. Microchimica Acta. 1967, 55 (6): 1126–1135. S2CID 98540174. doi:10.1007/BF01225955.
[5]
Di Maio, V. J. M. Gunshot Wounds: Practical aspects of firearms, ballistics, and forensic techniques 2nd. CRC. 1998: 341. ISBN 0-8493-8163-0.
[6]
Glover, R. L. Detecting lead in "arrow" wounds in deer using rhodizonic acid. Wildlife Society Bulletin. 1981, 9 (3): 216–219. JSTOR 3781843.
[7]
Heller, J. F. Die Rhodizonsäure, eine aus den Produkten der Kaliumbereitung gewonnene neue Säure, und ihre chemischen Verhältnisse [Rhodizonic acid, one of the new acids derived from potassium preparations, and its chemical composition]. Justus Liebigs Annalen der Pharmacie. 1837, 24 (1): 1–16 [2009-07-08]. （原始内容存档于2022-01-08）.
[8]
Turner, E.; Gregory, W.; Parnell, E. A.; Liebig, J.; Rogers, J. B. Elements of Chemistry. Thomas, Cowperthwait & Co. 1846 [2009-07-30]. （原始内容存档于2022-01-08）. When potassium is heated in carbonic acid gas, combination takes place, and a dark olive powder is formed, composed of carbonic oxide and potassium, in the proportion C₇O₇+K₃, or 7CO+3K. This substance is formed in large quantity in the preparation of potassium from carbonate of potash and charcoal, and is the source of great loss and inconvenience. No such compound is formed with sodium, for which reason that metal may be more cheaply prepared than potassium.
[9]
Löwig, C. Chemie der organischen Verbindungen [Chemistry of Organic Compounds]. Zürich: F. Schultess. 1839.
[10]
Hunter, R.; Morris, C. (编). Universal Dictionary of the English language. New York: Collier. 1900 [2009-08-07].
[11]
Preisler, P. W.; Berger, L. Preparation of Tetrahydroxyquinone and Rhodizonic Acid Salts from the Product of the Oxidation of Inositol with Nitric Acid. Journal of the American Chemical Society. 1942, 64 (1): 67–69. doi:10.1021/ja01253a016.
[12]
Feigl, F.; Oesper, R. E. Spot Tests in Organic Analysis. 1960 [2009-07-30]. （原始内容存档于2022-01-08）.
[13]
Gmelin, L.; Watts, H. Hand-book of Chemistry. Cavendish Society. 1856.
[14]
Chen, H.; Armand, M.; Courty, M.; Jiang, M.; Grey, C. P.; Dolhem, F.; Tarascon, J.-M.; Poizot, P. Lithium salt of tetrahydroxybenzoquinone: toward the development of a sustainable Li-ion battery. Journal of the American Chemical Society. 2009, 131 (25): 8984–8. PMID 19476355. doi:10.1021/ja9024897.
[15]
Wyrwas, R. B.; Chick Jarrold, C. Production of C
6O−
6 from oligomerization of CO on molybdenum anions. Journal of the American Chemical Society. 2006, 128 (42): 13688–9. PMID 17044687. doi:10.1021/ja0643927.
[16]
Iraci, G.; Back, M. H. The photochemistry of the rhodizonate dianion in aqueous solution. Canadian Journal of Chemistry. 1988, 66 (5): 1293. doi:10.1139/v88-209 .
[17]
Zhao, B.; Back, M. H. The photochemistry of the rhodizonate dianion in aqueous solution (PDF). Canadian Journal of Chemistry. 1991, 69 (3): 528 [2009-08-07]. doi:10.1139/v91-079. （原始内容 (PDF)存档于2012-07-07）.
[18]
Cowan, J. A.; Howard, J. A. K. Dipotassium rhodizonate. Acta Crystallographica. 2004, E60 (4): m511–m513. doi:10.1107/S160053680400529X .
[19]
Dinnebier, R. E.; Nuss, H.; Jansen, M. Disodium rhodizonate: a powder diffraction study. Acta Crystallographica. 2005, E61 (10): m2148–m2150. doi:10.1107/S1600536805030552.

[patton-1] [1]
Patton, E.; West, R. New aromatic anions. VIII. Acidity constants of rhodizonic acid. Journal of Physical Chemistry. 1970, 74 (12): 2512–2518. doi:10.1021/j100706a018.

[braga2-2] [2]
Braga, D.; Cojazzi, G.; Maini, L.; Grepioni, F. Reversible solid-state interconversion of rhodizonic acid H₂C₆O₆ into H₆C₆O₈ and the solid-state structure of the rhodizonate dianion C
6O2−
6 (aromatic or non-aromatic?). New Journal of Chemistry. 2001, 25: 1221−1223. doi:10.1039/b107317f.

[gelb1-3] [3]
Gelb, R. I.; Schwartz, L. M.; Laufer, D. A. The structure of aqueous rhodizonic acid. Journal of Physical Chemistry. 1978, 82 (18): 1985–1988. doi:10.1021/j100507a006.

[chalmers-4] [4]
Chalmers, R. A.; Telling, G. M. A reassessment of rhodizonic acid as a qualitative reagent. Microchimica Acta. 1967, 55 (6): 1126–1135. S2CID 98540174. doi:10.1007/BF01225955.

[5] [5]
Di Maio, V. J. M. Gunshot Wounds: Practical aspects of firearms, ballistics, and forensic techniques 2nd. CRC. 1998: 341. ISBN 0-8493-8163-0.

[Glover-6] [6]
Glover, R. L. Detecting lead in "arrow" wounds in deer using rhodizonic acid. Wildlife Society Bulletin. 1981, 9 (3): 216–219. JSTOR 3781843.

[heller-7] [7]
Heller, J. F. Die Rhodizonsäure, eine aus den Produkten der Kaliumbereitung gewonnene neue Säure, und ihre chemischen Verhältnisse [Rhodizonic acid, one of the new acids derived from potassium preparations, and its chemical composition]. Justus Liebigs Annalen der Pharmacie. 1837, 24 (1): 1–16 [2009-07-08]. （原始内容存档于2022-01-08）.

[turner-8] [8]
Turner, E.; Gregory, W.; Parnell, E. A.; Liebig, J.; Rogers, J. B. Elements of Chemistry. Thomas, Cowperthwait & Co. 1846 [2009-07-30]. （原始内容存档于2022-01-08）. When potassium is heated in carbonic acid gas, combination takes place, and a dark olive powder is formed, composed of carbonic oxide and potassium, in the proportion C₇O₇+K₃, or 7CO+3K. This substance is formed in large quantity in the preparation of potassium from carbonate of potash and charcoal, and is the source of great loss and inconvenience. No such compound is formed with sodium, for which reason that metal may be more cheaply prepared than potassium.

[loewig1-9] [9]
Löwig, C. Chemie der organischen Verbindungen [Chemistry of Organic Compounds]. Zürich: F. Schultess. 1839.

[hunter-10] [10]
Hunter, R.; Morris, C. (编). Universal Dictionary of the English language. New York: Collier. 1900 [2009-08-07].

[preisler-11] [11]
Preisler, P. W.; Berger, L. Preparation of Tetrahydroxyquinone and Rhodizonic Acid Salts from the Product of the Oxidation of Inositol with Nitric Acid. Journal of the American Chemical Society. 1942, 64 (1): 67–69. doi:10.1021/ja01253a016.

[feigl-12] [12]
Feigl, F.; Oesper, R. E. Spot Tests in Organic Analysis. 1960 [2009-07-30]. （原始内容存档于2022-01-08）.

[gmelinwa-13] [13]
Gmelin, L.; Watts, H. Hand-book of Chemistry. Cavendish Society. 1856.

[chen-14] [14]
Chen, H.; Armand, M.; Courty, M.; Jiang, M.; Grey, C. P.; Dolhem, F.; Tarascon, J.-M.; Poizot, P. Lithium salt of tetrahydroxybenzoquinone: toward the development of a sustainable Li-ion battery. Journal of the American Chemical Society. 2009, 131 (25): 8984–8. PMID 19476355. doi:10.1021/ja9024897.

[wyja-15] [15]
Wyrwas, R. B.; Chick Jarrold, C. Production of C
6O−
6 from oligomerization of CO on molybdenum anions. Journal of the American Chemical Society. 2006, 128 (42): 13688–9. PMID 17044687. doi:10.1021/ja0643927.

[iraci-16] [16]
Iraci, G.; Back, M. H. The photochemistry of the rhodizonate dianion in aqueous solution. Canadian Journal of Chemistry. 1988, 66 (5): 1293. doi:10.1139/v88-209 .

[zhao-17] [17]
Zhao, B.; Back, M. H. The photochemistry of the rhodizonate dianion in aqueous solution (PDF). Canadian Journal of Chemistry. 1991, 69 (3): 528 [2009-08-07]. doi:10.1139/v91-079. （原始内容 (PDF)存档于2012-07-07）.

[cowan-18] [18]
Cowan, J. A.; Howard, J. A. K. Dipotassium rhodizonate. Acta Crystallographica. 2004, E60 (4): m511–m513. doi:10.1107/S160053680400529X .

[dinne-19] [19]
Dinnebier, R. E.; Nuss, H.; Jansen, M. Disodium rhodizonate: a powder diffraction study. Acta Crystallographica. 2005, E61 (10): m2148–m2150. doi:10.1107/S1600536805030552.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]

[14]

[15]

[16]

[17]

[18]

[19]

盐

氧化和分解

酸

盐

Wikiwand in your browser!

玫棕酸

盐

氧化和分解

酸

盐

Wikiwand in your browser!

历史

化学性质

结构

参见

参考资料

玫棕酸


IUPAC名 5,6-Dihydroxycyclohex-5-ene-1,2,3,4-tetrone 5,6-二羟基-5-环己烯-1,2,3,4-四酮
别名	二羟基二喹啉二氧二醌玫瑰红酸
识别
CAS号	118-76-3（二水合物） ^Y
PubChem	67050
ChemSpider	60401
SMILES	C1(=C(C(=O)C(=O)C(=O)C1=O)O)O
InChI	1/C6H2O6/c7-1-2(8)4(10)6(12)5(11)3(1)9/h7-8H
InChIKey	WCJLIWFWHPOTAC-UHFFFAOYAV
EINECS	204-276-5
MeSH	C005690
性质
化学式	C₆H₂O₆
熔点	130 - 132 °C（271 K）
若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。