At least seven unknown compounds were observed in the DBDPE-exposed rats, indicating that DBDPE biotransformation occurred in rats. These compounds were identified by comparing relative retention times and full-scan mass spectra of DBDPE debrominated products from a photolytic degradation experiment using GC/EI-MS and GC/ECNI-MS analysis. The results showed that debromination of DBDPE to lower brominated BDPEs were not the primary metabolic pathway observed in rats. Two of the metabolites were proposed tentatively as MeSO(2)-nona-BDPE and EtSO(2)-nona-BDPE using GC/EI-MS, but their structures require further confirmation by other techniques and authentic standards. In addition, evidence of a biological response to DBDPE and BDE-209 and their metabolites in rats are different.
The present study assessed and compared the oxidative and reductive biotransformation of brominated flame retardants, including established polybrominated diphenyl ethers (PBDEs) and emerging decabromodiphenyl ethane (DBDPE) using an in vitro system based on liver microsomes from various arctic marine-feeding mammals: polar bear (Ursus maritimus), beluga whale (Delphinapterus leucas), and ringed seal (Pusa hispida), and in laboratory rat as a mammalian model species. Greater depletion of fully brominated BDE209 (14-25% of 30 pmol) and DBDPE (44-74% of 90 pmol) occurred in individuals from all species relative to depletion of lower brominated PBDEs (BDEs 99, 100, and 154; 0-3% of 30 pmol). No evidence of simply debrominated metabolites was observed. Investigation of phenolic metabolites in rat and polar bear revealed formation of two phenolic, likely multiply debrominated, DBDPE metabolites in polar bear and one phenolic BDE154 metabolite in polar bear and rat microsomes. For BDE209 and DBDPE, observed metabolite concentrations were low to nondetectable, despite substantial parent depletion. These findings suggested possible underestimation of the ecosystem burden of total-BDE209, as well as its transformation products, and a need for research to identify and characterize the persistence and toxicity of major BDE209 metabolites. Similar cause for concern may exist regarding DBDPE, given similarities of physicochemical and environmental behavior to BDE209, current evidence of biotransformation, and increasing use of DBDPE as a replacement for BDE209.
IDENTIFICATION AND USE: Decabromodiphenyl ethane (DBDPE) has been used as a substitute for decabrominated diphenyl ether (BDE-209) and therefore it is currently used in more or less the same applications as BDE-209, such as manufacture of plastics (including polyester and vinyl ester resins) and rubber products, as well as in different applications related to manufacture of textiles and leather. This compound is also found in polymers used for electronic and electrical applications. DBDPE could also be used in adhesives and sealants. HUMAN STUDIES: When tested in vitro in HepG2 cells, DBDPE was cytotoxic with anti-proliferation effect and apoptosis was accompanied with overproduction of reactive oxygen species. ANIMAL STUDIES: Male rats were orally administrated with 100 mg/kg DBDPE for 90 days. Results showed DBDPE was found in all tissues. At least seven unknown compounds were observed in the DBDPE-exposed rats, indicating that DBDPE biotransformation occurred in rats. In mice treated with DBDPE for 30 days the levels of alanine aminotransferase or ALT and aspartate aminotransferase or AST of higher dose treatment groups were markedly increased. Blood glucose levels of treatment groups were higher than those of control group. There was also an induction in TSH, T3, and fT3. Uridinediphosphoglucuronosyltransferase (UDPGT), 7-pentoxyresorufin O-depentylase (PROD), and ethoxyresorufin-O-deethylase (EROD) activities were found to have been increased significantly in the high dose group. Histopathologic liver changes were characterized by hepatocyte hypertrophy and cytoplasmic vacuolization. In rats, DBDPE induced oxidative stress, elevated blood glucose levels, increased CYP2B2 mRNA, CYP2B1/2 protein, PROD activity, and induced CYP3A2 mRNA, CYP3A2 protein, and luciferin benzylether debenzylase (LBD) activity. No evidence of maternal toxicity, developmental toxicity, or teratogenicity was observed in rats or rabbits treated with DBDPE at dosage levels up to 1,250 mg/kg-day. DBDPE was not genotoxic in bacterial assays (Ames/Salmonella typhimurium and Escherichia coli WP2 reverse mutation assays) and no chromosomal aberrations were reported in Chinese hamster lung cells. ECOTOXICITY STUDIES: In Grass carp (Ctenopharyngodon idella) 5 miRNAs were significantly down-regulated and 36 miRNAs were significantly up-regulated after DBDPE exposure indicating that miRNAs have potential for use as biomarkers. The fish hepatocyte assay, based on the synthesis and secretion of vitellogenin from isolated male liver cells produced a clear dose-response curve in the presence of DBDPE. DBDPE induced the induction of hepatic EROD activity at low test concentrations, but started to inhibit the activity at higher concentrations. Also, the induction of the hepatocyte conjugation activity, UDPGT, was induced with no signs of inhibition even at the highest test concentration. The reduced EROD activity resulted in a drop in the production of vitellogenin by the cells. In vivo tests showed that DBDPE was acutely toxic to water fleas, the 48 hr EC-50 value being 19 ug/L. Moreover, DBDPE reduced the hatching rates of exposed zebra-fish eggs and raised significantly the mortality of hatched larvae. Treatment-related effects were identified for E. fetida reproduction, C. sativa survival, and L. esculentum and A. cepa height and dry weight. The most sensitive endpoints were decreased height and dry weight for A. cepa and decreased reproduction for E. fetida.
/SRP:/ Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR if necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Poisons A and B/
/SRP:/ Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if needed. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 mL/kg up to 200 mL of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool ... . Cover skin burns with dry sterile dressings after decontamination ... . /Poisons A and B/
/SRP:/ Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Positive-pressure ventilation techniques with a bag valve mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Consider administering a beta agonist such as albuterol for severe bronchospasm ... . Monitor cardiac rhythm and treat arrhythmias as necessary ... . Start IV administration of D5W TKO /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Watch for signs of fluid overload ... . Treat seizures with diazepam (Valium) or lorazepam (Ativan) ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Poisons A and B/
/ALTERNATIVE and IN VITRO TESTS/ OBJECTIVE: To investigate the toxic effects of decabromodiphenyl ethane (DBDPE), used as an alternative to decabromodiphenyl ether in vitro. METHODS: HepG2 cells were cultured in the presence of DBDPE at various concentrations (3.125-100.0 mg/L) for 24, 48, and 72 hr respectively and the toxic effect of DBDPE was studied. RESULTS: As evaluated by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide and lactate dehydrogenase assays and nuclear morphological changes, DBDPE inhibited HepG2 viability in a time- and dose-dependent manner within a range of 12.5 mg/L to 100 mg/L and for 48 hr and 72 hr. Induction of apoptosis was detected at 12.5-100 mg/L at 48 h and 72 hr by propidium iodide staining, accompanied with overproduction of reactive oxygen species (ROS). Furthermore, N-acetyl-L-cysteine, a widely used ROS scavenger, significantly reduced DBDPE-induced ROS levels and increased HepG2 cells viability. CONCLUSION: DBDPE has cytotoxic and anti-proliferation effect and can induce apoptosis in which ROS plays an important role.
来源:Hazardous Substances Data Bank (HSDB)
吸收、分配和排泄
DBDPE和BDE-209在大鼠体内的分布和毒性研究
Male rats were orally administrated with corn oil containing 100 mg/kg bw/day of DBDPE or BDE-209 for 90 days, after which the levels of DBDPE and BDE-209 in the liver, kidney, and adipose were measured. Biochemical parameters, including thyroid hormone levels, 13 clinical chemistry parameters, and the mRNA expression levels of certain enzymes were also monitored. Results showed DBDPE was found in all tissues with concentrations 3-5 orders of magnitude lower than BDE-209.
/MILK/ We have examined several emerging brominated flame retardants (BFRs) including 2-ethyl-1-hexyl-2,3,4,5-tetrabromobenzoate (TBB), bis(2-ethylhexyl) tetrabromophthalate (TBPH), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), 4,5,6,7-tetrabromo-1,1,3-trimethyl-3-(2,3,4,5-tetrabromophenyl)-indane (OBIND), and decabromodiphenyl ethane (DBDPE) in paired human maternal serum (n = 102) and breast milk (n = 105) collected in 2008-2009 in the Sherbrooke region in Canada. Three legacy BFRs were also included in the study for comparison: decabromobiphenyl (BB-209), 2,2',4,4',5,5'-hexabromobiphenyl (BB-153), and 2,2',4,4',5,5'-hexabromodiphenyl ethers (BDE-153). TBB, BB-153, and BDE-153 had detection frequencies greater than 55% in both serum and milk samples. Their lipid weight (lw) adjusted median concentrations (ng g(-1) lw) in serum and milk were 1.6 and 0.41 for TBB, 0.48 and 0.31 for BB-153, and 1.5 and 4.4 for BDE-153, respectively. The detection frequencies for the other BFRs measured in serum and milk were 16.7% and 32.4% for TBPH, 3.9% and 0.0% for BTBPE, 2.0% and 0.0% for BB-209, 9.8% and 1.0% for OBIND, and 5.9% and 8.6% for DBDPE. The ratio of TBB over the sum of TBB and TBPH (fTBB) in serum (0.23) was lower than that in milk (0.46), indicating TBB has a larger tendency than TBPH to be redistributed from blood to milk. Overall, these data confirm the presence of non-PBDE BFRs in humans, and the need to better understand their sources, routes of exposure, and potential human health effects
来源:Hazardous Substances Data Bank (HSDB)
吸收、分配和排泄
十溴二苯基乙烷（DBDPE），作为十溴二苯基醚（deca-BDE）的替代品，在中国圈养的中国短吻鳄中进行了研究。在成年鳄鱼的组织、幼鳄和鳄鱼蛋中均检测到了DBDPE，其浓度分别为4.74-192、0.24-1.94和0.01-0.51 ng g(-1) 脂肪重量。与PBDEs（多溴联苯醚）和PCBs（多氯联苯）相比，中国短吻鳄中的DBDPE污染有限。此外，成年鳄鱼肌肉中的DBDPE浓度比幼鳄和鳄鱼蛋中的浓度高出1到3个数量级，这表明在中国短吻鳄中DBDPE的母体传递潜力有限。
Decabromodiphenyl ethane (DBDPE), a replacement for decabromodiphenyl ether (deca-BDE), was investigated in captive Chinese alligators from China. DBDPE was detected in adult tissues, neonates and eggs of Chinese alligators with concentrations ranging from 4.74-192, 0.24-1.94, and 0.01-0.51 ng g(-1) lipid weight, respectively. Compared to PBDEs and PCBs, DBDPE contamination was limited in Chinese alligators. Additionally, DBDPE concentrations in adult muscles were one to three orders of magnitude higher than those in neonates and eggs, suggesting the limited maternal transfer potential of DBDPE in Chinese alligators. ...
Hen muscle, eggs, and newborn chick tissues (muscle and liver) were collected from an electronic waste recycling site in southern China. The authors examined the maternal transfer, potential metabolism, and tissue distribution of several halogenated flame retardants (HFRs) during egg formation and chicken embryo development. The pollutant composition changes significantly from hen muscle to eggs and from eggs to tissues of newborn chicks. Higher-halogenated chemicals, such as octa- to deca-polybrominated diphenyl ether (PBDE) congeners, deca-polybrominated biphenyl (PBB209), and dechlorane plus (DP), are less readily transferred to eggs compared with lower-halogenated chemicals. During embryo development, PBDEs are the most likely to be metabolized, whereas decabromodiphenyl ethane (DBDPE) is the least. The authors also observed selective maternal transfer of anti-DP and stereoselective metabolism of syn-DP during chicken embryo development. During tissue development, liver has greater affinity than the muscle for chemcials with a high log octanol-water partition coefficient, with the exception of DBDPE. The differences in metabolism potential of different chemicals in chicken embryos cause pollutant composition alterations. Halogenated flame retardant from maternal transfer and tissue distribution also exhibited chemical specificity, especially for DBDPE. Levels of DBDPE were elevated along with the full process from hen muscle to eggs and from eggs to chick tissues. ...
The extensive use of polybrominated diphenyl ethers (PBDEs) and decabromodiphenyl ethane (DBDPE) has made them widespread contaminants in abiotic environments, but data regarding their bioavailability to benthic organisms are sparse. The bioaccumulation potential of PBDEs and DBDPE from field-collected sediment was evaluated in the oligochaete Lumbriculus variegatus using a 49-d exposure, including a 28-d uptake and a 21-d elimination phase. All PBDEs and DBDPE were bioavailable to the worms with biota-sediment accumulation factors (BSAFs) ranging from 0.0210 g organic carbon/g lipid to 4.09 g organic carbon/g lipid. However, the bioavailability of highly brominated compounds (BDE-209 and DBDPE) was poor compared with that of other PBDEs, and this was confirmed by their relatively low freely dissolved concentrations (C(free)) measured by solid-phase microextraction. The inverse correlation between BSAFs and hydrophobicity was explained by their uptake (k(s)) and elimination (k(e)) rate constants. While ke changed little for PBDEs, ks decreased significantly when chemical hydrophobicity increased. The difference in bioaccumulation kinetics of brominated flame retardants in fish and the worms was explained by their physiological difference and the presence of multiple elimination routes. The appropriateness of 28-d bioaccumulation testing for BSAF estimation was validated for PBDEs and DBDPE. In addition, C(free) was shown to be a good indicator of bioavailability.
Reaction of 2,3,4,5,6-pentabromobenzyl bromide with 2,4,6-triphenylpyranyl
作者：A. A. Burtasov、A. N. Mishunyaeva、M. K. Pryanichnikova、V. N. Shishkin、B. S. Tanaseichuk
DOI：10.1007/s11176-005-0019-2
日期：2004.9
The main process in the reaction of 2,4,6-triphenylpyranyl with 2,3,4,5,6-pentabromobenzyl bromide in 2-propanol is electron transfer to give 2,4,6-triphenylpyrylium bromide and 2,3,4,5,6-pentabromobenzyl radical.
[EN] FLAME RETARDANTS, PREPARATION METHODS, AND THERMOPLASTIC COMPOSITIONS THEREOF<br/>[FR] AGENTS IGNIFUGEANTS, LEURS PROCÉDÉS DE PRÉPARATION ET COMPOSITIONS THERMOPLASTIQUES ASSOCIÉES
申请人：DUPONT CHINA RES & DEV AND MAN CO LTD
公开号：WO2015180165A1
公开（公告）日：2015-12-03
Disclosed are flame retardants comprising compounds of Formula (1), wherein the polyol is a disaccharide or a C12 sugar alcohol, which has at least one glucose or one fructose unit per molecule, R1is H or CH3;R2is H or CH3;mis an integer ranging from 6 to 9; and n is an integer ranging from 2 to 9. Also disclosed are methods for producing the inventive flame retardants, thermoplastic compositions and articles comprising the same, and methods for improving flame retardancy of thermoplastic polymers using the same.
The invention is a flame retardant for styrene foams. The flame retardant contains both aromatic bromine and an olefin. The olefin is an internal olefin. Desirable flame retardants are selected from:
formula I:
wherein R
1
is C
1
-C
6
and optionally containing a heteroatom or olefin; R
2
is C
1
-C
6
and optionally containing a heteroatom or olefin; and R
3
-R
12
is H, C
1
-C
6
(optionally containing a heteroatom), or halogen; and further wherein the compound of formula I is present in a concentration of at least 50 percent of a trans isomer;
formula II:
wherein R
1
is Halogen, C
1
-C
6
and optionally containing a heteroatom or olefin; R
2
is Halogen, C
1
-C
6
and optionally containing a heteroatom or olefin; and R
3
-R
7
is H, C
1
-C
6
(optionally containing a heteroatom), or halogen; and
formula III:
wherein R
1
is Halogen, C
1
-C
6
and optionally containing a heteroatom or olefin; R
2
is Halogen, H, C
1
-C
6
and optionally containing a heteroatom or olefin; and R
3
-R
6
is H, halogen.
PREPARATION AND PROVISION OF HIGH ASSAY DECABROMODIPHENYLETHANE
申请人：Hussain Saadat
公开号：US20080227903A1
公开（公告）日：2008-09-18
High assay, reaction-derived decabromodiphenylethane product is prepared by feeding (i) diphenylethane or (ii) partially brominated diphenylethane having an average bromine number less than about two, or (iii) both of (i) and (ii), into the liquid confines of a reaction mixture. Such reaction mixture is (a) formed from components comprised of excess liquid bromine and aluminum-based Lewis acid bromination catalyst, and (b) maintained at one or more elevated reaction temperatures of from about 45°-90° C., and at least when elevated pressure is needed to keep a liquid state in the reaction mixture at the temperature(s) used, the reaction mixture is at such an elevated pressure, whereby ar-bromination occurs. The feeding is conducted at a rate slow enough to form high assay reaction-derived decabromodiphenylethane product, which is an effective flame retardant.
Process for separation of bromine from gaseous hydrogen bromide and use of such process in production of decabromodiphenylethane
申请人：Albemarle Corporation
公开号：US07408088B1
公开（公告）日：2008-08-05
Bromine is scrubbed from a gaseous mixture of bromine and hydrogen bromide by passing the mixture into a mixture formed from (i) diphenylethane and/or partially brominated diphenylethane with average bromine number less than about 2 and (ii) a catalytic quantity of iron and/or iron halide in which the halogen atoms are bromine atoms and/or chlorine atoms. Component (i) is brominated, and during such bromination, the mixture is kept hot enough to melt the organics to provide a liquid phase in the scrubber. Gaseous mixtures of bromine and hydrogen bromide are formed in processes of the invention in which decabromodiphenylethane products are produced using the partially brominated diphenylethane as feed to the bromination, which is conducted using an aluminum-based catalyst. Effective ways of removing iron catalyst residues from partially brominated diphenylethane or from decabromodiphenylethane product are also described.
