塩化アリル 化学特性,用途語,生産方法
外観
無色～わずかにうすい黄色, 澄明の液体
溶解性
水に難溶 (0.36g/100ml水, 20℃)。エタノール、クロロホルム、エーテルに可溶。水に微溶。
用途
エピクロロヒドリン、グリセリン、アリルアミン、ポリマー、樹脂の合成原料 (CHAPMAN(VER.16:2, 2009))
化学的特性
Allyl chloride is a colorless liquid, insoluble in water but soluble in common organic solvents.
Allyl chloride is prepared by the reaction of propylene with chlorine. It is a common
alkylating agent relevant to the manufacture of pharmaceuticals and pesticides. It is also a
component in some thermo-setting resins. Allyl chloride has been produced commercially since 1945 and is used almost exclusively as a chemical intermediate, principally in the
production of epichlorohydrin or as a raw material for epichlorohydrin. It is also used as
a chemical intermediate in the preparation of glycerin, glycerol chlorohydrins, glycidyl
ethers, allylamines, and allyl ethers of trimethylpropane, sodium allyl sulfonate, a series of
allyl amines and quaternary ammonium salts, allyl ethers, and a variety of alcohols, phenols,
and polyols. It is also used in pharmaceuticals as a raw material for the production of
allyl isothiocyanate (synthetic mustard oil), allyl substituted barbiturates (sedatives), and
cyclopropane (anesthetic); in the manufacture of specialty resins for water treatment and
to produce babiturate and hypnotic agents such as aprobarbital, butalbital, methohexital
sodium, secobarbital, talbutal, and thiamyl sodium.
物理的性質
Colorless to light brown to reddish-brown liquid with a pungent, unpleasant, garlic-like odor. An
experimentally determined odor threshold concentration of 470 ppb
v was reported by Leonardos et
al. (1969).
来歴
Allyl chloride, the only chloropropene of industrial importance, was first produced in 1857 by A. CAHOURS and A. W. HOFMANN by reacting phosphorus chloride with allyl alcohol. The name allyl is derived from the latin allium, meaning garlic. Inhalation of even small amounts of allyl chloride produces, after a short time, the characteristic odor of garlic on the breath. At the end of the 1930s, IG Farbenindustrie and the Shell Development Co. developed the high-temperature chlorination of propene, permitting large-scale production of allyl chloride with good yields. A significant part of the development was done by the Shell Chemical Co. when erecting a commercial plant in 1945. Dow, Solvay, and Asahi-Kashima developed their own processes.
使用
Allyl chloride (3-chloropropene; 1-chloro-2-propene) is a chemical intermediate used in the synthesis of allyl compounds found in varnish, resins, polymers, pesticides, and pharmaceuticals (O’Neil, 2001).
調製方法
Allyl chloride can be synthesized by reaction of allyl alcohol with HCl or by treatment of allyl formate with HCl in the presence of a catalyst (ZnCl2).
一般的な説明
A clear colorless liquid with an unpleasant pungent odor. Flash point -20°F. Boiling point 113°F. Less dense than water (7.8 lb / gal) and insoluble in water. Hence floats on water. Vapor irritates skin, eyes and mucous membranes. Vapors are heavier than air. Long exposure to low concentrations or short exposure to high concentrations may have adverse health effects from inhalation or skin absorption.
空気と水の反応
Highly flammable. Insoluble in water.
反応プロフィール
Allyl chloride presents a serious fire and explosion hazard when exposed to heat, flame or oxidizing agents. Polymerizes violently and exothermically with Lewis acids (aluminum chloride, boron trifluoride, sulfuric acid) or metals (aluminum, magnesium, zinc, or galvanized metal) [MCA SD-99, 1973]. Incompatible with acids (nitric acid, chlorosulfonic acid, oleum), with strong bases (sodium hydroxide, potassium hydroxide), with ethyleneimine and ethylenediamine [Lewis, 3rd ed., 1993, p. 36]. Attempts to alkylate benzene or toluene using Allyl chloride in the presence of ethylaluminum chlorides have led to explosions.
危険性
Skin and eye irritant. Upper respiratory
tract irritant, liver and kidney damage. Question-
able carcinogen.
健康ハザード
Allyl chloride is toxic and flammable. Exposures to allyl chloride cause a cough, sore throat,
headache, dizziness, weakness, respiratory distress, abdominal pain, burning sensation,
vomiting, and loss of consciousness. After acute inhalation exposures to high levels of
allyl chloride, workers developed irritation of the eyes and respiratory passages, loss of
consciousness, and fatal injury. Prolonged and intense exposure produced conjunctivitis,
reddening of eyelids, and corneal burn, damage to the CNS, causing motor and sensory
neurotoxic damage, and the heart and respiratory system, causing the onset of pulmonary
edema in humans. Laboratory rabbits exposed to allyl chloride through inhalation developed
degenerative changes that included dilation of sinusoids and vacuolar degeneration
in the liver, congestion or cloudy swelling and fatty degeneration of the epithelium of the
renal convoluted tubules, and thickening of the alveolar septa in the lungs. The exposed cat
exhibited only muscle weakness and unsteady gait toward the end of the exposure period.
火災危険
Special Hazards of Combustion Products: Releases irritating hydrogen chloride gas on combustion
毒性学
Acute and Subacute Toxicity: LD50=460 mg/kg (rat, oral); LD50= 3.7 mg/kg (rabbit, percutaneous); LC50= 11 mg/L (rat, inhalation, 2 h). The inhalation of 3 ppm allyl chloride during 7 h/d on 5 days a week was tolerated by a group of rats, guinea pigs, and rabbits for 180 days without irreversible damage occurring. An analogous test using 8 ppm over a period of 35 days led to damage of the liver and kidneys. Further experiments demonstrate a neurotoxic effect of allyl chloride, in particular to the peripheral nerves of cats and rabbits.
職業ばく露
Allyl chloride is used as a chemical intermediate and in making allyl compounds, epichlorohydrin, and glycerol.
発がん性
The IARC found that it could not
classify AC as a human carcinogen on the basis of available
data. In contrast, EPA considers AC to be a possible
human carcinogen and has ranked it in EPA’s Group
C. This classification was based on a low
incidence of forestomach tumors in female mice and positive
results in a variety of genetic toxicity tests. However, the
forestomach tumor data were not used for quantitative cancer
risk assessment. AC is a strong alkylating agent and is
structurally similar to other forestomach carcinogens, such
as propylene oxide and epichlorohydrin, which cause tumors
at the site of exposure.
Olsen reported on a cohort of 1064 men employed at a
Texas plant in epoxy resin, glycerin, andAC/epichlorohydrin
production between 1957 and 1986 and followed up through
1989. There were 66 total deaths [standardized mortality
ratio (SMR)=0.8; 95% CI 0.6–1.0] and 10 cancers
(SMR=0.5; CI 0.2–0.9).However, the authors noted that the
cohort was limited due to sample size, duration of follow-up,
small numbers of deaths both expected and found, and the
limited exposure potential.
環境運命予測
Biological. Bridié et al. (1979) reported BOD and COD values of 0.23 and 0.86 g/g using
filtered effluent from a biological sanitary waste treatment plant. These values were determined
using a standard dilution method at 20 °C and stirred for a period of 5 d. When a sewage seed was
used in a separate screening test, a BOD value of 0.42 g/g was obtained. The ThOD for allyl
chloride is 1.67 g/g.
Photolytic. Anticipated products from the reaction of allyl chloride with ozone or OH radicals in
the atmosphere are formaldehyde, formic acid, chloroacetaldehyde, chloroacetic acid, and
chlorinated hydroxy carbonyls (Cupitt, 1980).
Chemical/Physical. Hydrolysis under alkaline conditions will yield allyl alcohol (Hawley,
1981). The estimated hydrolysis half-life in water at 25 °C and pH 7 is 2.0 yr (Mabey and Mill,
1978).
輸送方法
UN1100 Allyl chloride, Hazard Class: 3; Labels: 3-Flammable liquid, 6.1-Poisonous materials
純化方法
Likely impurities include 2-chloropropene, propyl chloride, iso-propyl chloride, 3,3-dichloropropane, 1,2-dichloropropane and 1,3-dichloropropane. Purify it by washing with conc HCl, then with Na2CO3 solution, dry it with CaCl2, and distil it through an efficient column [Oae & Vanderwerf J Am Chem Soc 75 2724 1953]. [Beilstein 1 IV 738.] LACHRYMATORY, TOXIC.
不和合性
Contact with water forms hydrochloric acid. Keep away from strong oxidizers, acids, aluminum, amines, peroxides, chlorides of iron and aluminum; magnesium, zinc.
廃棄物の処理
Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Controlled incineration at a temperature of 982 C for 2 seconds minimum.
塩化アリル 上流と下流の製品情報
原材料
準備製品
4-アセチル安息香酸エチル
フタル酸ジアリル
3'-シアノアセトフェノン
チオスルタップナトリウム塩標準品
2-[[2-(2-プロペニルオキシ)フェノキシ]メチル]オキシラン
2-(1-hydroxy-3-butenyl)-5-methyl furan
3-(ブロモアセチル)安息香酸
1,2-ジブロモ-3-クロロプロパン
rac-(R*)-2-メチル-3-アリル-4-オキソ-2-シクロペンテン-1-オール
1-[3-(トリフルオロメチル)フェニル]-3-クロロ-4-(クロロメチル)ピロリジン-2-オン
1-アリル-2-チオ尿素
1,4-ジヒドロ-2,6-ジメチル-4-(3-ニトロフェニル)-3,5-ピリジンジカルボン酸3-メチル5-(2-ブロモエチル)
Flocculant ST
5-ジメチルアミノ-1,2,3-トリチアン
fixing agent TCD-R
エニルコナゾール
1,3-ジクロロプロペン (cis-, trans-混合物)
1,5-ヘキサジエン
チオシクラム·しゅう酸
2-(アリルオキシ)フェノール
アリルマグネシウムクロリド
カルバミン酸tert-ブチル
1-クロロ-2-プロパノール (約25%2-クロロ-1-プロパノール含む)
1,2,3-トリクロロプロパン
オイゲノール
4-フェニル-1-ブテン
N,N-ジメチルアリルアミン
3-(2-メチル-1,3-チアゾール-4-イル)安息香酸
1,3-ジクロロ-2-プロパノール
3-アセチル安息香酸
アリルアミン
エピクロロヒドリン
1-ブロモ-3-クロロプロパン
1-クロロ-2-メチル-2-フェニルプロパン
POLY DIMETHYL DIALLYL AMMONIUM CHLORIDE
3-シアノフェナシルブロミド