N,N-ジメチルアニリン 化学特性,用途語,生産方法
外観
無色～うすい黄色, 澄明の液体
溶解性
水に不溶。アルコール, エーテルに易溶。エタノール及びアセトンに極めて溶けやすく、水に溶けにくい。
解説
N,N-ジメチルアニリン，C8H11N(121.18)．C6H5N(CH3)2．アニリンのN,N-ジメチル体．工業的には，アニリンと大過剰のメタノールに少量の硫酸を加えてオートクレーブ中で加熱してつくられる．液体．融点2.5 ℃，沸点192～193 ℃．77 ℃(1.73 kPa)．水蒸気蒸留できる．0.9557．1.5582．pKa 5.15(25 ℃)．ほとんどの有機溶媒にまじるが，水に不溶．ニトロソ化するとp-ニトロソ体が容易にでき，またホスゲンと縮合させるとミヒラーケトンが得られる．塩基性染料，アゾ染料の中間物となる
用途
塩基性染料?有機ゴム薬品(加硫促進剤)中間体、溶剤
化学的特性
N,N-Dimethylaniline is a light yellow to light brown oily liquid. Has a pungent odor. Soluble in ethanol, chloroform, ether and aromatic organic solvents, slightly soluble in water.It is a tertiary amine used in the synthesis of several triarylmethane dyes like malachite green. It is also used in the synthesis of a magnetic gram stain for the detection of bacteria.
物理的性質
Straw to brown-colored oily liquid with a characteristic amine-like odor. Odor threshold
concentration is 13 ppb (quoted, Amoore and Hautala, 1983).
使用
N,N-dimethylaniline is an important dye intermediate. It can be used to prepare alkaline yellow, Crystal Violet 5BN, basic magenta green, basic lake blue BB, basic brilliant blue R, cationic red 2BL, brilliant red 5GN, violet 3BL, brilliant blue, etc. In the pharmaceutical industry, the product can be used to manufacture cefazolin V, sulfamonomethoxine, Sulfadoxine, fluorocytosine, etc. moreover, It can be used as an intermediate to vanillin, a stabilizer for colorimetric peroxidase determination or as a reagent in chemical synthesis.
定義
ChEBI: N,N-dimethylaniline is a tertiary amine that is aniline in which the amino hydrogens are replaced by two methyl groups. It is a tertiary amine and a dimethylaniline.
調製方法
N,N-Dimethylaniline is made by heating aniline, methyl alcohol and sulfuric acid under pressure, followed by hydrolysis of the sulfate formed with sodium hydroxide to the free base (Windholz et al 1983). United States production in 1975 was estimated at 4,600 metric tons (HSDB 1989).
一般的な説明
N,N-Dimethylaniline appears as a yellow to brown colored oily liquid with a fishlike odor. Less dense than water and insoluble in water. Flash point 150°F. Toxic by ingestion, inhalation, and skin absorption. Used to make dyes and as a solvent.
空気と水の反応
Insoluble in water.
反応プロフィール
Explosive decomposition occurred when finely divided benzoyl peroxide was allowed to react with N,N-Dimethylaniline by breaking an ampoule containing 0.5 grams of dimethylaniline in an autoclave, NFPA 491M, 1991. This result may be expected with other peroxides and various oxidants.
健康ハザード
Clinical signs of intoxication with N,N-dimethylaniline in man are headaches, cyanosis, dizziness, labored breathing, paralysis and convulsions (HSDB 1989). It is absorbed through the skin to produce a dangerous methemoglobinemia (Gosselin 1984). Treatment is similar to that of aniline with the object of managing methemoglobinemia.
火災危険
Combustible material: may burn but does not ignite readily. When heated, vapors may form explosive mixtures with air: indoors, outdoors and sewers explosion hazards. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form.
工業用途
N,N-Dimethylaniline is used as chemical intermediate in the manufacturing of vanillin, Michler's ketone, and dyes such as Acid Red 2, Basic Green 4 and Basic Violet 1 (Northcott 1978). It is also used as a solvent and an activator for polyesters and as an alkylating agent (Beard and Noe 1981). It is used as an acid scavenger or accepter in the manufacture of beta-lactam antibiotics such as penicillin and cephalosporin (Nachtmann and Gstrein 1981).
安全性プロファイル
Suspected carcinogen
with equivocal tumorigenic data. Human
poison by ingestion. Moderately toxic by
inhalation and skin contact. A skin irritant.
Human systemic effects by ingestion: nausea
or vomiting. Physiological action is similar
to, but less toxic than, adne. A central
nervous system depressant. Mutation data
reported. Flammable liquid when exposed to
heat, flame, or oxidizers. Explodes on
contact with benzoyl peroxide or
disopropyl peroxydicarbonate. To fight fire,
use foam, CO2, dry chemical. When heated
to decomposition it emits htghly toxic fumes
of adne and NOx. See also ANILINE.
発がん性
A 2-year corn oil gavage bioassay conducted by NTP in
F344/N rats (0.3 or 30 mg/kg) and B6C3F1 mice (0, 15, or
30 mg/kg) for 103 weeks concluded that there was some
evidence of carcinogenic activity for male F344/N rats as
indicated by the increased incidences of sarcomas or osteosarcomas
in the spleen; there was no evidence of carcinogenic
activity in the female rats or male mice; there was
equivocal evidence of carcinogenic activity for female mice
as indicated by an increased incidence of squamous cell
papillomas of the forestomach. Both rats and mice could
have tolerated doses higher than those used in these
studies.
環境運命予測
Photolytic. A rate constant of 1.48 x 10
-10 cm
3/molecule?sec was reported for the reaction of
N,N-dimethylaniline and OH radicals in air at room temperature (Atkinson et al., 1987).
Chemical/Physical. Products identified from the gas-phase reaction of ozone with N,Ndimethylaniline
in synthetic air at 23 °C were: N-methylformanilide, formaldehyde, formic acid,
hydrogen peroxide, and a nitrated salt having the formula: [C6H6NH(CH3)2]+NO3
- (Atkinson et al.,
1987). Reacts with acids forming water-soluble salts.
代謝
Ν,Ν-Dimethylaniline undergoes N-demethylation, N-oxidation, and ring hydroxylation in animals. Urinary metabolites produced by dogs and rabbits injected with this compound included 4-aminophenol, 4-dimethylaminophenol, 2-aminophenol and N-methylaniline (Williams 1959; Kiese and Renner 1974). N-oxidation, N-demethylation and ring hydroxylation of Ν,Ν-dimethylaniline was demonstrated in vitro using liver microsomal preparations from pigs, rats, rabbits, chickens, and guinea pigs (Fish et al 1955; Zeigler and Pettit 1964, 1966; Abou-Donia and Menzel 1968). N-oxidation was also demonstrated using whole homogenate of human liver (Zeigler and Gold 1971; Rane 1974). Evidence has been obtained with rabbit liver microsomes for two pathways for Ν,Ν-dimethylaniline N-oxidation (Hlavica and Kehl 1977). One pathway involves cytochrome P-450 while the second makes use of flavin-containing monooxygenase. N,N-Dimethylaniline was also metabolized to formaldehyde in the nasal and respiratory mucosa of Fischer 344 rats (McNulty et al 1983). Alveolar type II cells from rabbit and rat lungs catalyzed the N-oxidation of this compound (Devereux and Fouts 1974; Ohmiya and Mehendale 1981). The microsomal preparation from rat seminal vesicles when fortified with arachidonic acid catalyzed the dealkylation of N,Ndimethylaniline (Sivarajah et al 1982).
参考文献
N,N-Dimethylaniline and 1-(trifluoromethyl)benzene-functionalized tetrakis(ethynyl)pyrenes: synthesis, photophysical, electrochemical and computational studies DOI:
10.1016/J.TET.2011.12.066Friedel-Crafts Reaction of N,N-Dimethylaniline with Alkenes Catalyzed by Cyclic Diaminocarbene-Gold(I) Complex doi:
10.1038/s41598-018-29854-0Groundwater Chemicals Desk Reference DOI:
10.5860/choice.27-6127Patty's Toxicology 6-Volume Set-Wiley (2012)
Proctor Proctor and Hughes' chemical hazards of the workplace (5th edn) Wiley Interscience DOI:
10.1002/JAT.1034Nitrogen and phosphorus solvents DOI:
10.1016/c2009-0-01359-2Purification of Laboratory Chemicals DOI:
10.5860/choice.50-6768
N,N-ジメチルアニリン 上流と下流の製品情報
原材料
準備製品
4-クロロ-2-(トリフルオロメチル)ピリミジン
N6,N6-ジメチルアデニン
6-(ヘプチルチオ)-1H-プリン
メチルレッド
オーラミン
4-エチル-2-ピリジンアミン
4, 4^<'^>-dimethylamino diphenyl ketone
3-[[[N-エチル-[4-[4-ジエチルアミノ-4'-[[3-(ソジオオキシスルホニル)ベンジル](エチル)アミノ]ベンズヒドリリデン]-2,5-シクロヘキサジエン-1-イリデン]イミニウム]-N-イル]メチル]ベンゼンスルホン酸アニオン
2,4-ジニトロベンズアルデヒド
4-CHLORO-2,6-BIS(TRIFLUOROMETHYL)PYRIMIDINE
2,4-ジクロロ-5-フルオロピリミジン
メチレンブルー
ベーシック ブルー 26
Magentagreencrystals
2,6-ジメトキシピリミジン-4-カルボン酸
5-ブロモ-4,6-ジクロロピリミジン
メチルバイオレットBベース
N-ヘキシル-1H-プリン-6-アミン
Basic Dyestuff
4-ブロモ-N,N-ジメチルアニリン
6-エトキシ-1H-プリン
ビス[4-(ジメチルアミノ)フェニル]メタン
9H-プリン-6-カルボニトリル
N,N-ジメチル-3-ニトロアニリン
N,N,N',N'-テトラメチルベンジジン
ヤヌス グリーン B
6-benzylaminopurine
ミフェプリストン
2-アミノ-7-メチルヒポキサンチン
6-(エチルスルファニル)-1H-プリン
Basic Blue 53
Basic Red 22
4-ジメチルアミノベンゼンジアゾスルホン酸 ナトリウム
leucotrope O
2-AMINO-3,5-DICHLORO-4,6-DIMETHYL PYRIDINE
N,N'-ジメチル-m-フェニレンジアミン
2,4-DICHLORO-6-FLUOROPYRIMIDINE
6-ブトキシ-1H-プリン
(3-メチルフェニル)カルバミド酸3-[(メトキシカルボニル)アミノ]フェニル
6-ヨード-1H-プリン