Document 15yann28waM0EdV1773N0wVod

II. HALOGENATED OLEFINIC HYDROCARBONS :; - 1. HALOGENATED ETHENE DERIVATIVES J ^ A. Monohalogenated Ethane Derivatives Vnrrt Chloride /k u & - JVw*-*-' ^ y y y ' Chemistry,--Vinyl chloride, chloroethylene, CH,--CHC1, has the molecular weight 62.50. It is a gas of the specific gravity 0.908 25/25 which solidifies at --160* C. and boils at --12 C. It is slightly soluble in water, soluble in alcohol, and very soluble in ether. It polymerizes when exposed to light, and its flammability limits are between 4 and 21.7 percent in air (Jones, 1938). It is used in the synthesis of organic com pounds such as resins. Schaumann (1934) determined vinyl chloride in blood* by evacuating 5 to 10 cc. of the latter in the Van Slvke apparatus, mixing the liberated blood gases with oxygen, decomposing the chlorinated hydrocarbon over heated platinum, absorbing the liberated hydrochloric acid in Pregl's "sodium carbonate-bisulfite solution" and determining the chlorine titrimetrically by Volhard's method. Regarding its absorption, fata, and excretion it has been shown that it is readily absorbed through the lungs and promptly excreted by this route, 32 percent being eliminated from the blood 10 minutes after discontinu ation of the narcosis as shown by Schaumann' (1934). Like other chlorinated hydrocarbons, vinyl chloride has narcotic prop erties. According to Peoples and Leake (1933) the narcotic range for mice is between 3.5 and 5 mM per liter of air. Concentrations of 7 mil per liter of air will cause narcosis in rabbits and dogs after 1 minute, and the recovery is prompt and not followed by untoward effects even after prolonged exposure. Schaumann (1934) determined the vinyl chloride level in the blood of cats anesthetized with 10 to 13 vol. percent as 15 to 17 mg. percent. Oster, Carr, Krantz, Jr., and Sauerwald (1947) used vinyl chloride stabilized with 0.5 percent of p-tert-butyl-catechol for narcosis of dogs, starting with concentrations of 50 vol. percent and reducing the concentration gradually to 7 voL percent. They found that the induction was rapid, but that "crowing" continued even during deep anesthesia and that there was profuse salivation. During narcosis the relaxation of the abdominal muscles was good but the legs remained rigid showing, through out the anesthesia, incoordinated movements. The recovery was rapid but associated with violent excitation. As to the effect of vinyl chloride on the circulation, Schaumann (1934) studied its effects in the Starling heart-lung preparation of cats judging the action by the effect on the intra-auricular pressure. He found rhat iy e. u< 195 ucc 057523 i v:i t. ' , i; x , Ii *. -!i i* ii ir >-: /< I1 T similar effects were produced by 1.3 percent of solaesthin (dichloroethylene), 3 voL percent of ether, and IS vol. percent of vinyl chloride. Higher concentrations (20 vol. percent) of vinyl chloride caused a more or less marked relative insufficiency and even 25 to 30 vol. percent were unable to produce complete cardiac failure. Oster, Carr, Krantz, Jr., and Sauerwald (1947) studied the circulatory response in dogs anesthetized with 10 vol. percent of vinyl chloride. They noted a moderate fall of the blood pressure and definite evidence of cardiac irregularities as indicated by intermittent tachycardia, extraventricular systoles and vagal beats. Electrocardiographic studies revealed marked changes of the cardiac rhythm such as tachycardia followed by bradycardia, inversion of the K spike, and in one instance incipient ventricular fibrillation. All records showed abnormalities of the QRS interval varying from sinus arrhythmia and transitory extreme left axis deviation to very serious conditions such as auricular-ventricular block, ventricular tachycardia, ventricular multi form extrasystoles, and inversion of the T wave with elevated ST segment in lead II. As the anesthesia progressed towards respiratory failure most of the QRS abnormalities disappeared but the R amplitude was generally reduced. As to the toxicity of vinyl chloride, Patty, Taut, and Waite (1930) studied this in guinea pigs. They found that exposure to 20 to 40 vol. percent kills the animals in a very short time, that concentrations of 10 voL percent are dangerous to life with exposures for 30 to 60 minutes, and that 0.5 voL percent is the maximum allowable concentration for several hours' exposure without causing acute disturbances of severe na ture. Animals exposed in this way showed some edema of the lungs and hyperemia of liver and kidneys. They considered vinyl chloride less harmful than chloroform or carbon tetrachloride and of a similar order of toxicity as ethyl chloride. Schaumann (1938) found that mice and rats tolerate repeated light narcosis for 4 hours daily on 5 to 8 consecutive days and for 1 hour daily for 4 weeks without showing kidney or liver injuries. Bogs which had been narcotized for 3 hours with 10 vol. percent on 7 occasions in the course of several weeks showed no considerable changes in kidney and liver. Higher concentrations (20 vol. percent) caused in dogs marked salivation, respiratory arrest, and vomiting after narcosis. Peoples and Leake (1933) determined the lethal range for mice with 10 minutes' exposure as 10 to 12 mM per liter, and Schaumann (1934) de termined the vinyl chloride level in the blood at the time of cardiac orrest as <40 mg. percent and at the time of respiratory arrest as 27 to 30 mg. percent, the same value for chloroform being 60 to 70 mg. percent. Regarding the toxicity of vinyl chloride for man, Patty, Yant, and Waite (1930) expressed the opinion that the gas does not possess adequate warning properties because of its odor or irritant action, but that it gives warning by producing symptoms of dizziness and disorientation in advance of harm, except when present in exceedingly high concentrations which would cause almost immediately helplessness and unconsciousness. Inhalation of 2.5 percent will soon cause dizziness, disorientation, and a burning sensation in the soles of the feet, which symptoms disappear im mediately after discontinuation of the exposure except for a slight head ache which may last 30 minutes. These authors suggested the use of 196 4 ; ' i ] * j < r J vinyl chloride for i as nercotic concent r percent may be dan and Sauerwald (19 effects on the circi. Industrial Hygienis continued exposure. , .>. Coni. Got. Iod. H 29 1953 Jon**. G. W.. Cbem. Re> Oat*r. R. H, C. J. Carr 1947. Patty. F. A, W. P. Tin Peoples. 3. A and C. D Schaumann. O, Medizii Schaumann, O., ace E LAaunga mittel, 3. Sp Yinvl bromide, bi 106.96. It is a liqu at --137.8 C. and t with alcohol and eth According to A'i anesthetic concentrr tolerated concentret determined the inor with vinyl bromide pared with 0.165 -- C indicating the great Abren, B. B., S. A. Pe. 1939. Abren, B. E. and G. A. Vinyl fluoride, fl 46.044. It is a gas v According to Les; cent lose their postu and with 80 vol. pen tion the animals be to fresh air, even af pulmonary irritatio* Lester, D. and L. A. G __ z. ^7aL.4^ ..r .. <- ucc 057524 (dichloroethyldoride. Higher i a more or lees ent were unable rantz, Jr., and )gs anesthetized lerate fall of the ties as indicated nd vagal beats, of the cardiac version of the E 3n. All records 'nus arrhythmia conditions such itricular multiTed ST segment ry failure most i was generally Waite (1930) 0 20 to 40 voL, atrations of 10 to 30 minutes, centration for 1 of severe nathe lungs and 1 cliloride less imilar order of mice and rats p-aecutive days liver injuries. . percent on 7 arable changes caused in after narcosis, mice with 10 m (1934) deof cardiac artsz as 27 to 30 ng. percent. y, Tant, and s=ess adequate : that it gives .tation in adoncentrations .onsciousness. tation, and a ;!=appear im: slight headi the use of vinyl chloride for narcosis in man, and Schaumann (1938) considered as narcotic concentrations for man 7 to 10 voL percent, whereas IS voL 'crcent may be-dangerous. In the opinion of Oster, Carr, Krantz, Jr., and Sauerw&ld (1947) it is not suitable for this purpose because of its effects on the circulation. The American Conference of Government Industrial Hygienists (1953) accepted 200 p. p. m. as threshold limit for continued exposure. BIBLIOGRAPHY jd. Cent. Got. Ind. Hygienists, Lot Angeles (1983), Area. Iod. Hyg. Occ. Mad., 8, 296,1983. Jones, G. W., Chem. Bevlew, IS, 1,1933. Oster, R. a, C. J. Carr, J. C. Krantz, Jr- and 1L J. Sauer*aid, AnesthezInL, 8, 388, 1947. Patty, F. A- W. P. Tant, and C. P. Waits, Pnb. Health Hep- 4J. 1983,1930. Peoples, 3. A and C. D. Leake. J. Pharm. ExptL Ther- 48, 284,1983. Schaumann. O., Medlsln a. Chemle, *, 139.1934. Schsumaan, O- eee K. B. Lehmann nnd 7. Ftnj, ToxlkoL u. Hyg. 4. tsehnlschan LSiungs mittel, J. Springer, Berlin, 1933, p. 130. Vettl Baoxme Vinyl bromide, bromoethylene, CH"CHBr, his the molecular weight 106.96. It is a liquid of the specific gravity 1.529 ll*/4* which solidifies at --137.8* C. and boils at 15.8* C. It is insoluble in water but miscible with alcohol and ether. According to Abreu, Peoples, and Emerson (1939), the minimal anesthetic concentration for mice is 3.5 mM per liter, and the highest tolerated concentration is 7 mil per liter. Abreu and Emerson (1940) determined the inorganic bromide content of the liver of mice narcotized with vinyl bromide as 0.043^0.0005 mg. per 1 gm. of wet tissue as com pared with 0.165^0.006 found in animals narcotized with ethyl bromide, indicating the greater stability of the unsaturated compound. BIBLIOGRAPHY Ahreu, B. E- 3. A. Peoples, mad G. A. Emerson. Anesthesia sad Analgesia, 18, 158, 1939. Abreu, B. E. and G. A Emerson. Ualv. Calif. Publ. Pharmacol- 1, 313, 1940. VnTTL FlUORIDC Vinyl fluoride, fluoroethylene, CHj-CHF, has the molecular weight 46.044. It is a gas which boils at -- 51" C. According to Lester and Greenberg (1950) rats exposed to 60 voL per cent lose their postural reflexes, with 70 vol. percent their righting reflexes, and with 80 vol. percent their corneal reflexes. With the latter concentra tion the animals became dyspneic, but recovered fully when transferred to fresh air, even after 12^ hours' exposure, without showing evidence of pulmonary irritation. REFERENCE Lester, D. and L. A. Greenberg. Arch. Ind, Hyg. Occ. Med.. 2, 333, 1950.