Miscible with acetone, benzene, carbon tetrachloride, heptane, methanol (Worthing and Hance,
1991), methylene chloride, chloroform, trichloroethylene, and 1,1,2,2-tetrachloroethane.
暴露限值：
ACGIH TLV: TWA 1 ppm for cis and trans isomers (adopted).
物理描述：
1,3-dichloropropene appears as a clear colorless liquid. Flash point 95°F. Denser (at 10.2 lb / gal) than water and insoluble in water. Vapors are heavier than air. Used to make other chemicals and as soil fumigant.
颜色/状态：
Colorless to straw-colored liquid
气味：
Pungent odor
味道：
Bitter
熔点：
-50.0 °C
蒸汽密度：
1.4 AT 37.8 °C (AIR= 1)
蒸汽压力：
34.3 mm Hg at 25 °C (cis isomer), 23.0 mm Hg at 25 °C (trans isomer)
亨利常数：
0.00 atm-m3/mole
大气OH速率常数：
1.12e-11 cm3/molecule*sec
稳定性/保质期：
Stable under recommended storage conditions.
分解：
DT50 11.3 day (pH 5-9, 20 °C).
腐蚀性：
Corrosive to aluminum, magnesium, and alloys of these metals
Groups of 3-9 male Fischer 344 rats (200-260g) were admin 50 mg cis-1,3-dichloropropene (94.1% cis- & 2.5% trans-) or 50 mg trans-1,3-dichloropropene (97.3% trans- & 0.8 cis-)/kg bw, by gavage. The rats were sacrificed at various intervals after dosing, to determine the tissue non-protein sulfhydryls (NPS) in the liver, kidneys, forestomach, glandular, stomach, & bladder. Blood samples were also taken to determine the presence of unchanged 1,3-dichloropropene. Cis-1,3-dichloropropene was only detected in the blood (6.58 ug/liter) 15 min after dosing, the blood levels of trans-1,3-dichloropropene were 11.72 & 8.38 ug/liter, respectively, 15 & 45 min after dosing. A statistically significant decr in the non-protein sulfhydryl contents of the liver, kidneys, forestomach, & glandular stomach was found. This depletion reached a max, approx 2 hr after dosing. No depletion was noted in the bladder. It is not possible to distinguish the effects of cis- & trans-1,3-dichloropropene on NPS, as the results for the individual isomers were not reported. The results indicated that orally admin 1,3-dichloropropene produces a rapid & significant depletion of tissue non-protein sulfhydryls in the rat.
The metabolism of cysteine S-conjugates of both cis and trans-1,3-dichloropropene in the presence of rat kidney microsomes and purified flavin containing monooxygenase from hog liver was investigated in vitro. Putative S-oxide metabolites of cysteine S-conjugates were chemically synthesized, and diastereomers were separated and identified by spectroscopic means. The metabolic products of cysteine S-conjugates were identified by comparing the chemical properties of the metabolites with authentic synthetic cysteine S-conjugate S-oxides. S-conjugate S-oxygenase activity was not observed with rat kidney microsomes but was present when cysteine S-conjugates were incubated with the highly purified flavin containing monooxygenase from hog liver. The kinetic parameters indicated that considerable S-oxygenase stereoselectivity and structural selectivity was observed: cis cysteine S-conjugates were preferred substrates and N-acetylation of cysteine S-conjugates decreased substrate activity. S-Oxygenation was considerably diastereoselective and diastereoselectivity was much greater for cysteine S-conjugates with higher Vmax values. Cysteine S-conjugate S-oxides were not indefinitely stable, and under certain conditions, the S-oxides under- went a (2,3)-sigmatropic rearrangement to acrolein. Formation of acrolein or other electrophilic products from S-(chloropropenyl)cysteine conjugate S-oxides may contribute to the renal effects observed for S-(chloropropenyl)cysteine conjugates. Thus, cytotoxicity studies with isolated rat proximal tubular cells or LLC-PK1 cells treated with cysteine S-conjugates showed a time and dose dependent decrease in cell viability. Reduction of renal cytotoxicity of cysteine S-conjugates in the presence of methimazole, an alternate substrate competitive inhibitor of the flavin-containing monooxygenase, suggested that this enzyme may contribute to the renal effects of 1,3-dichloropropene.
The biotransformation to sulfur containing products of the Z-isomers & E-isomers of 1,3-dichloropropene administered ip in combination to male Wistar-rats was investigated. The presence of mercapturic acids in the urine of the animals was determined using GC with nitrogen & sulfur selective detection (GC-NDP & GC-FDP, respectively) & GC/MS with negative chemical ionization & single ion detection. Quantification of mercapturic acids in the urine of animals treated with the dichloropropene isomers in doses of 5 ug each, was achieved with the use of GC-NDP & GC-FPD, while GC/negative chemical ionization/MS detected only the mercapturic acids generated by doses = 25 ug or higher, due to the interference of endogenous products. Both products tested are metabolized via glutathione conjugation, with the generation of 2 major mercapturic acid conjugates, & that all three analytical procedures tested are useful for the determination of human exposure to low levels of 1,3-dichloropropene.
The major metabolic pathway is rapid conjugation with glutathione, resulting in the formation of a mercapturic acid metabolite that is excreted in the urine. Trans-1,3-Dichoropropene may also undergo hydrolysis and dechlorination to form 1-chloroallyl alcohol, an intermediate that reacts with alcohol dehydrogenase to form 1-chloroacrolein. Another minor pathway involves reaction with cytochrome P450 to form mutagenic cis and trans epoxides that convert to the mutagen 3-chloro2- hydroxy-propanal. Conjugation with glutathione can occur in the nasal tissue, kidney, and liver. The glutathione conjugate of cis-1,3-dichloropropene is then converted to the mercapturic acid and acetylated for excretion as the N-acetyl-cysteine metabolite. Alternative metabolic pathways for trans-1,3-dichloropropenes have also been proposed. reaction with cytochrome P-450 resulted in the formation of trans-1,3-dichloropropene epoxides. The trans-1,3-dichloropropene epoxides undergo hydrolysis, possibly catalyzed by epoxide hydrolase, to 3-chloro-2-hydroxypropanal (L893).
IDENTIFICATION: 1,3-Dichloropropene is a colorless to amber colored liquid with a penetrating, irritating, chloroform-like odor. It has been widely used in agriculture as a pre-plant soil fumigant for the control of nematodes in vegetables, potatoes, and tobacco. It often appears as part of a mixture also including 1,2-dichloropropane. Application is primarily by soil injection. In water, 1-3-dichloropropene is likely to disappear rapidly, because of its relatively low water solubility and high volatility. HUMAN EXPOSURE: The exposure of the general population through air, water, or food is unlikely. Occupational exposure is likely to be through inhalation and via the skin. Irritation of the eyes and the upper respiratory mucosa appears promptly after exposure. Dermal exposure caused severe skin irritations. Inhalation may result in serious signs and symptoms of poisoning with lower exposures resulting in depression of the central nervous system and irritation of the respiratory system. Some poisoning incidents have occurred in which persons were hospitalized with signs and symptoms of irritation of the mucous membrane, chest discomfort, headache, nausea, vomiting, dizziness and, occasionally, loss of consciousness and decreased libido The fertility status of workers employed in the production of chlorinated three-carbon compounds was compared with a control group. There was no indication of an assocation between decreased fertility and exposure. ANIMAL STUDIES: The acute oral toxicity of 1,3-dichloropropene in animals is moderate to high. Acute dermal exposure is moderately toxic. Acute intoxication showed central nervous and respiratory system involvement. Severe reactions were seen in rabbit skin and eye irritation tests. Degeneration of the olfactory epithelium and hyperplasia were seen in inhalation studies with mice and rats. Cis- and trans-1,3-dichloropropene and mixtures were mutagenic in bacteria with, and without, metabolic activation. In mice, increased incidences of hyperplasia of the urinary bladder, the forestomach, and the nasal mucosa were observed. There was an increase in the incidence of benign lung tumors. Some toxic changes in the olfactory mucosa of the nasal cavity were also seen in rats, but no increase in tumor incidence. The major metabolic route of elimination of 1,3-dichloropropene is via conjugation with glutathione.
The primary toxic effects of trans-1,3-dichloropropene are portal-of-entry effects resulting from the chemical reactivity of the compound and its physicochemical properties. Repeated irritation results in a hyperplastic response in the target tissues. The mutagenicity of trans-1,3-dichloropropene is attributed to its biotransformation by cytochrome P-450 to stereospecific epoxides and the hydrolysis product, 3-chloro-2-hydroxypropanal. It is likely that depletion of glutathione would block the major detoxification pathway for trans-1,3dichloropropene, resulting in increased toxicity of organs such as the liver and kidney because of binding of reactive intermediates to macromolecules in cells. There is some evidence that cytotoxicity of hepatic cells exposed to trans-1,3-dichloropropene is preceded by increased levels of phospholipid hydroperoxides (L893).
来源:Toxin and Toxin Target Database (T3DB)
毒理性
致癌性证据
A3：已确认的动物致癌物，对人类的相关性未知。/1,3-二氯丙烯/
A3: Confirmed animal carcinogen with unknown relevance to humans. /1,3-Dichloropropene/
Evaluation: No epidemiological data relevant to the carcinogenicity of 1,3-dichloropropene were available. There is sufficient evidence in experimental animals for the carcinogenicity of mixed isomers of 1,3-dichloropropene (technical grade). Overall evaluation: 1,3-Dichloropropene (technical grade) is possibly carcinogenic to humans (Group 2B). /1,3-Dichloropropene (technical grade)/
Following oral admin of 8.3-13.5 mg/kg body weight cis- or trans-2-(14)carbon-1,3-dichloropropene to rats, 80% of the radioactivity of the cis-isomer and 57% of the radioactivity of the trans-isomer was excreted in the urine within 24 hr. Little further urinary excretion occurred over the next 72 hr. After 96 hr, 2-5% of the cis-isomer and 23-24% of the trans-isomer were expired as (14)carbon carbondioxide; exhalation of other radioactive compounds was minor. Little fecal excretion was observed. Recovery of both isomers was about 90%.
... Rats were fed (14)carbon-labeled ... isomers of 1,3-dichloropropene and showed differences in their metabolism. With all compounds, 80-90% was eliminated in the first 24 hr. Major route of excretion was in the urine, where ... 56.5% of trans was found. The amount of (14)carbon dioxide excreted was 23.6%, with correspondingly less ... in the urine.
Tomato plants absorbed labeled cis- and trans-1,3-dichloropropene through their roots with max 1,3-dichloropropene absorbed and translocated after 2-4 hr and no 1,3-dichloropropene detected by 48 hr. 1,3-Dichloropropene was metabolized to trans-3-chloroallyl alcohol, part of which was converted to trans-3-chloroacrylic acid and 3-chloropropanol. At 12 and 24 hr after treatment both cis-1,3-dichloropropene and trans-1,3-dichloropropene disrupted the organellar structure of the chloroplasts and the rough endoplasmic reticulum of some plants. However, despite the disruption of normal cellular structure, cis-1,3-dichloropropene and trans-1,3-dichloropropene do not present residue problems and cause concern about their residue fate.
Following the oral administration to rats of (14)C labeled 1,2-dichloropropane, cis-1,3-dichloropropene, or trans-1,3-dichloropropene, 80-90% of the radioactivity was eliminated in the feces, urine and expired air within the first 24 hr. The urine was the major route of excretion in all three cases.
Direct, Mild, and General <i>n</i>-Bu<sub>4</sub>NBr-Catalyzed Aldehyde Allylsilylation with Allyl Chlorides
作者：Makeda A. Tekle-Smith、Kevin S. Williamson、Isaac F. Hughes、James L. Leighton
DOI：10.1021/acs.orglett.7b03193
日期：2017.11.3
A direct, mild, and general method for the enantioselective allylsilylation of aldehydes with allyl chlorides is reported. The reactions are effectively catalyzed by 5 mol % of n-Bu4NBr, and this rate acceleration allows the use of complex allyl donors in fragment-coupling reactions and of electron-deficient allyl donors. The results are (1) significant progress toward a “universal” asymmetric aldehyde
Chemo-, regio-, and stereoselective hydroboration of conjugated enyne alcohol/amine: facile synthesis of Z , Z -/ Z , E -1,3-dien-1/2-ylboronic ester bearing hydroxyl/amino group
Hydroboration of conjugated enyne alcohol/amine is studied by using copper salts and bis(pinacolato)diboron as pre-catalysts and boron source respectively. It is suggested that the chemo-selectivity is derived from a combined electronic influence of the heteroatoms on the substrate and the ligand on the transition metal. The regioselectivity is probably dominated mainly by electronic effect of the
Substituted 2-arylimino heterocycles and compositions containing them, for use as progesterone receptor binding agents
申请人：Bayer Corporation
公开号：US06353006B1
公开（公告）日：2002-03-05
This invention relates to 2-arylimino heterocycles, including 2-arylimino-1,3-thiazolidines, 2-arylimino-2,3,4,5-tetrahydro-1,3-thiazines, 2-arylimino-1,3-thiazolidin-4-ones, 2-arylimino-1,3-thiazolidin-5-ones, and 2-arylimino-1,3-oxazolidines, and their use in modulating progesterone receptor mediated processes, and pharmaceutical compositions for use in such therapies.
[EN] ORGANIC COMPOUNDS FOR APPLICATIONS IN BACTERIAL INFECTIONS TREATMENT<br/>[FR] COMPOSÉS ORGANIQUES DESTINÉS À ÊTRE APPLIQUÉS DANS LE TRAITEMENT D'INFECTIONS BACTÉRIENNES
申请人：NOVARTIS AG
公开号：WO2010031750A1
公开（公告）日：2010-03-25
The present application describes organic compounds that are useful for the treatment, prevention and/or amelioration of human diseases.
本申请描述了对治疗、预防及/or改善人类疾病的有机化合物。
Efficient Synthesis of Trifluoromethyl Amines through a Formal Umpolung Strategy from the Bench-Stable Precursor (Me<sub>4</sub>
N)SCF<sub>3</sub>
Reported herein is the one‐pot synthesis of trifluoromethylated amines at room temperature using the bench‐stable (Me4N)SCF3 reagent and AgF. The method is rapid, operationally simple and highly selective. It proceeds via a formal umpolung reaction of the SCF3 with the amine, giving quantitative formation of thiocarbamoyl fluoride intermediates within minutes that can readily be transformed to N‐CF3
