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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2015/03/07 15:25:13」(JST)

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Benzidine (trivial name), also called 4,4'-diaminobiphenyl (systematic name), is the organic compound with the formula (C₆H₄NH₂)₂. it is an aromatic amine. It is a component of a test for cyanide. Related derivatives are used in the production of dyes. Benzidine has been linked to bladder and pancreatic cancer.^[2]

§Synthesis and properties

Benzidine is prepared in a two step process from nitrobenzene. First, the nitrobenzene is converted to 1,2-diphenylhydrazine, usually using iron powder as the reducing agent. Treatment of this hydrazine with mineral acids induces a rearrangement reaction to 4,4'-benzidine. Smaller amounts of other isomers are also formed.^[3] The benzidine rearrangement, which proceeds intramolecularly, is a classic mechanistic puzzle in organic chemistry.^[4]

The conversion is described as a [5,5]sigmatropic reaction.^[5]^[6]

In terms of its physical properties, 4,4'-benzidine is poorly soluble in cold water but can be recrystallized from hot water, where it crystallises as the monohydrate. It is dibasic, the deprotonated species has K_a values of 9.3 × 10⁻¹⁰ and 5.6 × 10⁻¹¹. Its solutions react with oxidizing agents to give deeply coloured quinone-related derivatives.

§Applications

As with some other aromatic amines such as 2-Naphthylamine, benzidine has been significantly withdrawn from use in most industries because it is so carcinogenic. In the past, benzidine was used to test for blood. An enzyme in blood causes the oxidation of benzidine to a distinctively blue-coloured derivative. The test for cyanide relies on similar reactivity. Such applications have largely been replaced by methods using phenolphthalein/hydrogen peroxide and luminol.

§Related 4,4’-benzidines

A variety of derivatives of 4,4’-benzidine are commercially produced on the scale of one to a few thousand kilograms per year, mainly as precursors to dyes and pigments.^[3] These derivatives include, in order of scale, the following:

3,3'-Dichlorobenzidine
o-tolidine, 2,2'-dimethyl-4,4’-benzidine
o-dianisidine (2,2'-dimethoxy-4,4’-benzidine, CAS# 119-90-4, m.p. 133 °C)
3,3',4,4'-Tetraaminodiphenyl, precursor to polybenzimidazole fiber.

§Safety

In August 2010 benzidine dyes were included in the U.S. EPA's List of Chemicals of Concern.^[7] The manufacture of Benzidine has been illegal in the UK since at least 2002 under the Control of Substances Hazardous to Health Regulations 2002 (COSHH).

§References

^ ^a ^b "NIOSH Pocket Guide to Chemical Hazards #0051". National Institute for Occupational Safety and Health (NIOSH).
^ "Known and Probable Carcinogens". American Cancer Society. 2011-06-29.
^ ^a ^b Schwenecke, H.; Mayer, D. (2005). "Benzidine and Benzidine Derivatives". Ullmann’s Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a03_539.
^ March, J. (1992). Advanced Organic Chemistry (5th ed.). New York: J. Wiley and Sons. ISBN 0-471-60180-2.
^ Shine, H. J.; Zmuda, H.; Park, K. H.; Kwart, H.; Horgan, A. G.; Collins, C.; Maxwell, B. E. (1981). "Mechanism of the benzidine rearrangement. Kinetic isotope effects and transition states. Evidence for concerted rearrangement". Journal of the American Chemical Society 103 (4): 955–956. doi:10.1021/ja00394a047. .
^ Shine, H. J.; Zmuda, H.; Park, K. H.; Kwart, H.; Horgan, A. G.; Brechbiel, M. (1982). "Benzidine rearrangements. 16. The use of heavy-atom kinetic isotope effects in solving the mechanism of the acid-catalyzed rearrangement of hydrazobenzene. The concerted pathway to benzidine and the nonconcerted pathway to diphenyline". Journal of the American Chemical Society 104 (9): 2501–2509. doi:10.1021/ja00373a028.
^ "Benzidine Dyes Action Plan Summary". U. S. Environmental Protection Agency. 2010-08-18.

UpToDate Contents

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1. 膀胱癌のスクリーニング screening for bladder cancer
2. Epidemiology and risk factors of urothelial (transitional cell) carcinoma of the bladder
3. 先天性骨髄性ポルフィリン症 congenital erythropoietic porphyria

English Journal

Cross-linking of horseradish peroxidase adsorbed on polycationic films: utilization for direct dye degradation.

Bayramoglu G, Altintas B, Yakup Arica M.SourceBiochemical Processing and Biomaterial Research Laboratory, Faculty of Sciences, Gazi University, Teknik Okullar, 06500, Ankara, Turkey, g_bayramoglu@hotmail.com.
Bioprocess and biosystems engineering.Bioprocess Biosyst Eng.2012 Mar 27. [Epub ahead of print]
Horseradish peroxidase (HRP) was immobilized on the polyaniline (PANI) grafted polyacrylonitrile (PAN) films. The maximum HRP immobilization capacity of the PAN-g-PANI-3 film was 221 μg/cm(2). The HRP-immobilized PAN-g-PANI-3 film retained 79 % of the activity of the same quantity free enzyme. Th
PMID 22451080

Mechanism for the reaction of 2-naphthol with N-methyl-N-phenyl-hydrazine suggested by the density functional theory investigations.

Gao JY, Zhang CH, Luo MM, Kim CK, Chu W, Xue Y.SourceCollege of Chemistry, Key Lab of Green Chemistry and Technology in Ministry of Education, Sichuan University, Chengdu 610064, People's Republic of China.
Journal of computational chemistry.J Comput Chem.2012 Jan 15;33(2):220-30. doi: 10.1002/jcc.21967. Epub 2011 Nov 1.
For the first time the computed mechanisms for the novel reaction of 2-naphthol with N-methyl-N-phenylhydrazine, leading to 1-amino-2-naphthol (Tang et al., J Am Chem Soc 2008, 130, 5840), have been investigated using the density functional theory. Four distinct possible pathways were evaluated: two
PMID 22042734

Japanese Journal

Solution-Processed White Light-Emitting Diode Utilizing Hybrid Polymer and Red--Green--Blue Quantum Dots

Kwon Byoung Wook,Son Dong Ick,Park Dong-Hee [他],Choi Heon-Jin,Choi Won-Kook
Jpn J Appl Phys 51(9), 09MH03-09MH03-4, 2012-09-25
… The Al/Cs2CO3/[RGB CdSe/ZnS QDs+PVK]/poly[(N,N\aku '-bis(4-butylphenyl)-N,N\aku '-bis(phenyl)benzidine)] (poly-TPD)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/indium--tin-oxide (ITO)/glass WLEDs shows electroluminescence (EL) centered at around 474, 544, and 629 nm with CIE coordinates, (0.44,0.32) at the forward bias +11 V, which clearly reveals that CdSe/ZnS QDs existing at the interface between PVK plays as a recombination center of exciton. …
NAID 150000104060

Plasma-Etching of Spray-Coated Single-Walled Carbon Nanotube Films for Biointerfaces

Kim Joon Hyub,Lee Jun-Yong,Min Nam Ki
Jpn J Appl Phys 51(8), 08HE02-08HE02-5, 2012-08-25
… To demonstrate the effectiveness of plasma-etched SWCNT film electrodes as biointerfaces, Legionella antibody was selected as analysis model owing to its considerable importance to electrochemical biosensors and was detected using plasma-etched SWCNT film electrodes and a 3,3',5,5'-tetramethyl-benzidine dihydrochloride/horseradish peroxidase (TMB/HRP) catalytic system. …
NAID 40019395046

Swelling-induced long-range ordered structure formation in polyelectrolyte hydrogel

Arifuzzaman Md.,Wu Zi Liang,Kurokawa Takayuki,Kakugo Akira,Gong Jian Ping
Soft Matter 8(31), 8060-8066, 2012-08-21
… The hydrogel is synthesized from a cationic monomer, N-[3-(N,N-dimethylamino)propyl] acrylamide methyl chloride quaternary (DMAPAA-Q), in the presence of a small amount of the oppositely charged poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT) that has a semi-rigid nature. …
NAID 120005228646

Related Pictures

★リンクテーブル★

リンク元	「腎盂尿管癌」「ベンジジン」「4-aminobiphenyl」
拡張検索	「diaminobenzidine reaction」

「腎盂尿管癌」

Benzidine
Names
	IUPAC name 4,4'-diaminobiphenyl
	Other names Benzidine, di-phenylamine, diphenylamine, 4,4'-bianiline, 4,4'-biphenyldiamine, 1,1'-biphenyl-4,4'-diamine, 4,4'-diaminobiphenyl, p-diaminodiphenyl
Identifiers
CAS Registry Number	92-87-5
ChEMBL	ChEMBL15901
ChemSpider	6844
	InChI InChI=1S/C12H12N2/c13-11-5-1-9(2-6-11)10-3-7-12(14)8-4-10/h1-8H,13-14H2 ; Key: HFACYLZERDEVSX-UHFFFAOYSA-N ; InChI=1/C12H12N2/c13-11-5-1-9(2-6-11)10-3-7-12(14)8-4-10/h1-8H,13-14H2; Key: HFACYLZERDEVSX-UHFFFAOYAX ;
Jmol-3D images	Image
KEGG	C16444
PubChem	7111
	SMILES c2c(c1ccc(N)cc1)ccc(N)c2 ;
Properties
Molecular formula	C12H12N2
Molar mass	184.24 g/mol
Appearance	Grayish-yellow, reddish-gray, or white crystalline powder
Density	1.25 g/cm3
Melting point	122 to 125 °C (252 to 257 °F; 395 to 398 K)
Boiling point	400 °C (752 °F; 673 K)
Solubility in water	0.94 g/100 mL at 100 °C
Related compounds
Related compounds	biphenyl
Hazards
Main hazards	carcinogenic
	US health exposure limits (NIOSH):
PEL (Permissible)	occupational carcinogen
	Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
	verify (what is: /?)
	Infobox references

　　[★]

英: 腎盂癌 renal pelvic cancer; 尿管癌 ureter cancer, ureteric cancer
関: 腎尿路の腫瘍

疫学

50-70歳に多
男女比は2-4:1と男性に多い
腎盂腫瘍は腎腫瘍の約10%を占める
尿路上皮癌の4-5%

病因

タバコ、コーヒー、人工甘味料
化学発癌物質

芳香族アミン

2-naphthylamine

benzidine

薬剤

鎮痛剤(フェナセチン、アセトアミノフェン)
抗癌剤(シクロホスファミド)
造影剤(トロトラスト)

疾患

バルカン腎症

病理

1. 移行上皮癌が大部分

移行上皮癌(90%)、扁平上皮癌(3-10%)、腺癌や未分化癌(1%以下)

2. 多中心性で膀胱にも発生する (2割程度の症例で膀胱に併発)

症状

無症候性血尿
側腹部痛(血塊や腫瘍組織による尿路閉塞のため)
側腹部腫瘤形成

診断

1. 静脈性尿路造影(IVP,DIP)、逆行性腎盂造影、経皮的腎盂尿管造影

陰影欠損像や尿路閉塞所見

2. CT、MRI

腫瘍像、リンパ節転移、多臓器への転移の有無

3. 内視鏡

膀胱腫瘍と腎盂尿管腫瘍の確認

4. 尿細胞診

：陽性率は40-60%なので、腫瘍を疑った場合しつこくやる

(血管造影)

新生血管に乏しい

治療法

1. 根治的手術療法：腎尿管全摘除兼膀胱部分切除術
2. 保存的手術療法：開放手術、内視鏡手術

再発するので、結局1.をやらざるを得ないことが多いらしい

3. 非手術療法：多剤併用化学療法(M-VAC)、放射線療法
4. BCGの腎盂内注入療法：上部尿路のcarcinoma in situ(CIS)に対する治療

2/3の症例で癌が消えるらしい。

予後

表在性腫瘍は予後良好で、浸潤性腫瘍は予後不良
扁平上皮癌は予後不良
異型度、浸潤度どちらも5年生存率に影響する。
尿管は筋層が薄く、浸潤しやすいので、尿管癌が見つかった場合、浸潤度はT2以降である。

「ベンジジン」

　　[★]

英: benzidine
関: 芳香族アミン、労働基準法施行規則

概念

ベンジジン (benzidine) は、芳香族アミンの1種。IUPAC名は4,4'-ジアミノビフェニル。
国際がん研究機関によってヒトに対する発癌性が認められており、日本では労働安全衛生法によって試験研究用途以外での製造・輸入・譲渡・提供・使用が禁止されている[1]。

性質

純粋なものは常温で白色の固体であるが、空気および光で容易に酸化され暗赤色を呈する。水に不溶。
1960年代以降、ヒトに対する発癌性、特に膀胱癌を引き起こすことが明らかとなったため、各国の政府によって取扱いが厳しく規制されている。日本では1972年（昭和47年）に労働安全衛生法によって製造等が禁止されている[2]。

参考

1.

http://ja.wikipedia.org/wiki/%E3%83%99%E3%83%B3%E3%82%B8%E3%82%B8%E3%83%B3

「4-aminobiphenyl」

　　[★]

関: 膀胱癌

4-aminobiphenyl is an amine derivative of biphenyl. It is used to manufacture azo dyes. It is a known human carcinogen[2] and so it has been largely replaced by less toxic compounds. It is similar to benzidine.

参考

wikipedia en

http://en.wikipedia.org/wiki/4-Aminobiphenyl

chemical

http://www.scbt.jp/datasheet-216773-4-aminobiphenyl.html

「diaminobenzidine reaction」

　　[★] ジアミノベンジジン反応

[PGCH-1] "NIOSH Pocket Guide to Chemical Hazards #0051". National Institute for Occupational Safety and Health (NIOSH).

[2] "Known and Probable Carcinogens". American Cancer Society. 2011-06-29.

[Ullmann-3] Schwenecke, H.; Mayer, D. (2005). "Benzidine and Benzidine Derivatives". Ullmann’s Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a03_539.

[4] March, J. (1992). Advanced Organic Chemistry (5th ed.). New York: J. Wiley and Sons. ISBN 0-471-60180-2.

[5] Shine, H. J.; Zmuda, H.; Park, K. H.; Kwart, H.; Horgan, A. G.; Collins, C.; Maxwell, B. E. (1981). "Mechanism of the benzidine rearrangement. Kinetic isotope effects and transition states. Evidence for concerted rearrangement". Journal of the American Chemical Society 103 (4): 955–956. doi:10.1021/ja00394a047. .

[6] Shine, H. J.; Zmuda, H.; Park, K. H.; Kwart, H.; Horgan, A. G.; Brechbiel, M. (1982). "Benzidine rearrangements. 16. The use of heavy-atom kinetic isotope effects in solving the mechanism of the acid-catalyzed rearrangement of hydrazobenzene. The concerted pathway to benzidine and the nonconcerted pathway to diphenyline". Journal of the American Chemical Society 104 (9): 2501–2509. doi:10.1021/ja00373a028.

[7] "Benzidine Dyes Action Plan Summary". U. S. Environmental Protection Agency. 2010-08-18.

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