Document MMLbqGxdoXqo1Okwe0aby3xex

{ <i CW'U -fvaWJ C'1ETtr)r/U See Lithium bromoacetylide; Lithium chloroacetylide; bromoacetylide; Lithium trifluoropropynide See other haloacetylene derivatives, metal acetylides Sodium I /yhfe r/f/^ /1etps' DichJoroacetylene (Dichloroethyne) [7572*29-4] /?/i<-rto*'3 hjjrst ctiLorej/vA/zo ClCsCCl CzCI, /vJr&titL-) $- sv c 1. Wotiz, J. H. et al., J. Org, Chem., 1961, 26, 1626 2. Ott, E., Ber., 1942, 75, 1517 A-7TAc/iea yfTf(r 0*t/<.y 3. Kirk-Othmer, 1964, Vol. 5, 203-205 / 4. Siegel, J. et al, J. Org. Chem., 1970, 35, 3199 5. Riemschneider, R. et al., Ann., 1961, 640, 14 G (T/94J/0 U/A&f'VEP 6. MCA Case History No. 1989 7. Kende, A. S. et al., Synthesis, 1982, 455 8. Kende. A. S. et al., Tetrahedron Lett., 1982, 23, 2369, 2373 Dichloroacetylene is rather endothermic (AH? (g) +149.4 kJ/mol, 1.57 kJ/g) and a heat-sensitive explosive gas which ignites in contact with air. However, its azeotrope with diethyl ether (55,4% dichloroacetylene) is not explosive and is stable to air [1,2]. It is formed on catalysed contact between acetylene and -chlorine, or sodium hypochlorite at low temperature; or by the action of alkali upon polychloro-ethane and -ethylene derivatives, notably trichloroethylene [3]. A safe synthesis has been described [4]. Ignition of a 58 mol% solution in ether on exposure to air of high humidity, and violent explosion of a cone, solution in carbon tetrachloride shortly after exposure to air have been * ^HLoftor/tbst/z k/juL reported. Stirring the ethereal solution with tap water usually caused ignition and explosion [5], Dichloroacetylene had been collected without incident on 6 /ptrAcr Wtf'Xt CyfcAj 7/C pDryevluiowuesnoncgcaisnieontseamspaedrailtuutree sionlumtioenw. Watehrensethpearcaotoorl,inngqsuyisuteeminwuaiosamtcoiydiiefieudc by lowering the temperature in the water separator, liquid chloroacetylene xfAJQ y/Q | ExajriC&'tiC separated there and exploded when a stopcock was turned [6]. A safer low tjeA-ToFme s-r/xru^f /ftjT 4>e A P/fXUCS . h/.'l.'- temperature preparation of material free of trichloroethylene has been described [7,8]. See Tetrachloroethylene: Sodium hydroxide Trichloroethylene: Alkali, or: Epoxides See also Chlorocyanoacetylene See other haloacetylene derivatives 1 Chiorodifluoroacetyl hypochlorite [68674-44-2] C2a2F2Oj cicFjCo.oa Unstable above 22C and explosive in gas phase at pressures above 27 -63 mbar. See entry ACYl HYPOHAUTES (reference 1) 206 wm DO 072207 CONFIDENTIAL October 22, 1986 Brian Knowles Per/Tet Western Division CHLORINATED ORGANICS AND A STRONG BASE Brian, This is a summary of the information I have been able to find on the problem of contacting chlorinated organics with a strong base. All of these reactions have been documented in the past as a reactive chemicals problem. 2CHC1^ + 7NaOH --------> HCOONa + NaCl + CO + 4H20 Heat of Reaction - 30.6 Kcal/mole of NaOH - 107.1 Kcal/mole of CHCl^ Explosions were reported in Louisiana and Texas when CH2Cl2 containing CHCl, was passed through a flake caustic bed ana when NaOH was used instead of potash for removing HCl from chci3. NaOH + CHC1 - CC12 ---------- > CCl = CC1 + HCl + CHCl - CHCl ---------- > + chci2 + chci2 ----------> CH = CCl + HCl CHCl = CCl2 --------- > CC1 = CC1 + HCl + CHjCl - CHC1 - CH3 ---------- > chloropropenes -----------> (Dow MAFP Process) CH2C CH2 + CH C - CH3 Emmett Brown La AS &TL db DO 07??08 conftdfntt AL -2- 2. Analyze a sample from every car or truck using a positive identification procedure 3. Question and investigate anything unusual, i.e., fittings, physical properties, color, etc. 4. Document that identification has been completed before unloading is started. 5. Carry out an audit on a periodic basis to determine that these procedures are followed and their importance understood. CAUSTIC/CHLOROFORM REACTION In the January summary of reactive chemicals, an incident was reported in which SOOKj of chloroform with a high acidity was being reprocessed by passing it through a pot containing caustic flakes. Several hours later a violent explosion occurreo in the caustic pot which blew the 80 pound top about 35 feet. I hope this incident was not viewed as being due to the high acidity of the chloroforand caustic instead of the well known high energy gas generating reaction between caustic and chloroform. 7 NaOH + 2CHC1 3 HC02Na +6 NaCl + CO + 4H20 TheAHR for this reaction was calculated to be -30.6 kcals/mole of NaOH or -107.1 kcals/mole cf CHCl* Consequently, it is advisable that caustic and chloroform not be brought together'at any temperature unless precautions are made to_handle botn the heat and the large pressure generation. (Texas Division Report/TC-1020; 3- A drum labeled "Rubinate M," a polymeric isocyanate, ruptured at the bottom and was propelled into the ceiling of a vented hood enclosure. Approximately one hour before the incident, 15 gallons of a waste isocyanate was transferred to the drum which was thought to contain approximately 15 gallons of polymeric isocyanate. What was a possible cause for this incident and what corrective action would you recommend? `Z?-195-60l "ON UiVod vvrnpopq ympoid vno tdt llrDynnyn7om-^ dirsrnoi aSm.'oys pirr Sirrypirvp ofrs1,, no Moyyrjr.o^-ry nrr.trrryyppr v:j 'pyqvmm rtmyyo? uni*? i?pv7i n? piurmn piny pTsxrrwp 7q pyrtopT Ft7V 'pdddrvor oo p-movT him:r my 'Tvnoif fi vo? p-aa-imyrypim rwryr j? cu/ttvr yto~rty Ydyvm yyyyi yp-? p:nr Tcvra ~rrr o.'.oarpv p^yrtnwyiioTSp to pynopv Turnip ^yuvroffoory nyrrpT 7vrr?zr.'dyy? yum-nti vnp psinvyjoz yp?T pirn vzinrw vddoird v in- p^ysavjsv vo pPTOdmp 1177c you m< yna `Dpyncmp uoavso ptn? pxmodujoo xravn 7-yqrrj-ovm irv ir?oa u/i-oQ o? rzyrr.tvnpom- vyvm rytnrov Fnppnmp l/tm/m 'voyvm irymi ppymnviuyi'mop pm Irry.rsiTddv -jrrr,r :vomr,'r A, i Doug A Rausch Corp S&LP 2030 Willard H. Dow Center 6-0510 Du*> dmuSdJ For address change, new subscriber, extra copies, contact J irporate Safety & Loss, 2020 Dow Center, The Dow Chemical Company, Midland, Ml 48640. DO 070209 CONFIDENTIAL i 1 Though usually considered to be non-flammable in use, it has unusually wide flammability limits and can be ignited by a flame or other intense source. The 2 most recent Data Sheet is devoted to all aspects of laboratory use. Alkali 1. Fabian, F., private comm., 1960 2. ABCM Quart. Safety Summ., 1956, 27, 17 3. Anon., Jahresber.. 1978, 70 An emulsion, formed during extraction of a strongly alkaline liquor with trichloroethylene, decomposed with evolution of the spontaneously flammable gas, dichloroacetylene [1]. This reaction could also occur if alkaline metal stripping preparations were used in conjunction with trichloroethylene degreasing preparations, some of which also contain amines as inhibitors, which could also cause the same reaction [2]. Apparently accidental contact of the solvent with potassium hydroxide solution led to generation of flames in the charging port of a stirred reactor [3]. See also Tetrachloroethylene: Sodium hydroxide Aluminium See Aluminium: Halocarbons Epoxides Dobinson, B. et ai, Chem. & Jnd., 1972, 214 l-Chloro-2,3-epoxypropane, the mono- and di-2,3-epoxypropyl ethers of 1,4-butanediol, and 2.2-bis[4(2',3'-epoxypropoxy)phenyl]propane can, in presence of catalytic quantities of halide ions, cause dehydrochlorination of trichloroethylene to dichloroacetylene, which causes minor explosions when the mixture is boiled under reflux. A mechanism is discussed. See also Alkali, above Metals See Aluminium: Halocarbons Barium: Halocarbons Beryllium: Halocarbons Lithium: Halocarbons Magnesium: Halocarbons Titanium: Halocarbons Oxidants See Perchloric acid: Trichloroethylene Dinitrogen tetraoxide: Halocarbons Oxygen (Gas): Halocarbons Oxygen (Liquid): Halocarbons Water Brade, C., Chem. Tech. (Berlin), 1952, 4, 506--507 219 Tetrachloroethylene [127-18-4] CI2C=CCI2 c2cu {MCA SD-24,1971); HCS1980. 887; RSC Lab. Hazard Data Sheet No. 6,1982 Aluminium See Aluminium: Halocarbons Aluminium, Zinc oxide Katz, S. et al., Chem. Abs.. 1981, 94, 33106 The mixture is burned militarily to produce dense smoke. Dinitrogen tetraoxide See Dinitrogen tetraoxide: Halocarbons Metals See Barium: Halocarbons Lithium: Halocarbons Sodium hydroxide Mitchell. P. R., private comm., 1973 The presence of 0.5% of trichloroethylene as impurity in tetrachloroethylene during unheated drying over solid sodium hydroxide caused generation of dichloroacetylene. After subsequent fractional distillation, the volatile fore-run exploded. See Dichloroacetylene; also Trichloroethylene: Alkali See other haloalkenes 3-Chloro-3-trichloromethyldiazirine [35295-56-5] ,----------- , C13CC(C1)N=N C2Cl4N2 Liu, M. T. H., Chem. Eng. News. 1974, 52(36). 3 An ampoule of the compound exploded when scored with a file, indicating high shock-sensitivity. See other diazirines Hexachloroethane [67-72-1] HCS 1980, 530 CI3CCCI3 C2CI* 00 07??!1 CONFTDFNTTAL