Document Jrdpaa2kZ05KvZwEdkZGEoG4K

4 i $ -jf B.Al-l/jnAT^XjAROCLORi'CHEMISTRY. PART L ECHERS " i ? I* ' BTf *?0?'|?IS l^j?0LPED aroclor derivatives ' : | f i` RD-58-Int Report No. 1181 ( -fc ) August 1, 1958 , R5cE RESEARCH By: J. Dazzl Dayton, Ohio Chemists: J. Dazzl, G. E. Bennett a-1 n. E. Sham - X.f-r.TiSl Job Nos. 4-9261; 4-931C; 9378 11 DI STRIBUTI0N Organic Chemicals Division (a) J. H. Lum (b) M. C. Throdahl (c ) F . E . Z - envy Research an. 4 V r.K ! nee : i nr Di ,e) Milton Kos.min f) H. K. Nason !g) P. B. Sharp [h)t Extra i) Extra j) Extra (*) Research and Development Pi Its St. Louis St. Lo u* s St. Let:I 3 Day ton Day tor. S t. Louis Dayton Day ton Day ton Day ton St. Louis . "- ; * t if | i i f t fft! --iM ill 111 1*1 M DSW 621485 -* * IF 7 *: * '? ' STLCOPCB4095516 STLCOPCB4095517 Sf M ft S'5- ' 2 relates-Initial experiments with Aroclors as chemical intermediates. A specific objective was to convert Aroclors, a low cost Monsanto product, to ethers for test as functional fluids and dielectrics! Also reported is early scouting research on the conden sation of hydrolyzed Aroclors (diphenols) with ethylene cn.orohydrin, ethyl chloroace tate, and a dilsocyan^e? A program covering specific phases of this Aroclor cheml^w was submitted in four detailed merino (vt -i -x\ T , emistry With hydrolvzed Aroeln * .Later work ow an Organic Division Development item, is reported elsewhere (R-7). is report covers par November June :arried out tween i. i Trhui^ do u'Tit *t ooUn i |^. 4 tt. v priH' rt' < m i- | I l#'. fn<J . : . 1 ' - lVC6'i duty ji.1 ip DSW 621487 STLCOPCB4095518 : -: -S~, - jjs.-y*= i =g,~*ggMw~,j9gt.' _ .' Uj> . - -`;r *k ________ Highly ^chlorinated Aroclors such as 1271#?'|f 1270, 1268 and 5460 react smoothly at 170-220C in . i the presence of caustic with alcohols such as 2- ethylhexanol and butyl cellosolve to form the corres- w* & ponding diethers in high yields . _ Aroclor 5460 gives a mixture of di- and triethers. Aroclor 1262 and excess m-cresol gives a mixture of mono-, di-, and tricresyl ethers. To prepare mono-ether, a large excess of Aroclor 1254 was reacted with 2-ethylhexanol and caustic. No reaction took place between Aroclor 127C excess allyl alcohol, and caustic at reflux temperature, Ethylene glycol fails to form p-hydroxyethyl ether with Aroclor 1271 and 1268. Instead, conversion to the corresponding hydrolyzed Aroclor occurs. This unexpected observation led to our work on polychloroaiphenols from Arc-dors, and eventual transfer to Organic Chemicals Division Development. Glycerol, Immiscible with Aroclor 1268, failed to react and only a trace of partly hydrolyzed material was isolated. Glycols possessing isolated hydroxyl groups, such as 1,5~ pentanediol, ' form an ether alcohol, shown first on 1,2,4trichlorobenzene, a model compound. The single experiment gave 23$ conversion and 49$ yield of the 5~{2,4-dichlorophenoxy)pentanol. HYDROLYZED AROCLOR 1270 DERIVATIVES Scouting research demonstrates that ethylene chlorohydrin and alkyl chloro- acetates condense with hydrolyzed Aroclors to yield the corresponding ether alcohol (I) and ether acid (II). f i :- f i $ f - |i f f |f jl^f I : fit i C I DSW 621488 STLCOPCB4095519 *i NaC DNa + 2C1CH2CH20H Cl 31 Cl Cl i' i. r 4 + 2CICH2COOR ft '**&?- KOCH2CH2O 7--f V0CH2CH2OH roocch2o-^ -OCH2COOR Further studies are needed in order to secure samples sufficiently pure for evaluation in polymer formation. a new Lyurethane was prepared from hydrolyzed Aroclor 1270 and di Dcyanatodiphenylmethane. patent iisciosures were submitted on reported Aroclor chemis ` 1 i. ; f pftf _EVALU_A_T_I_O_N_ Replacement of two chlorine atoms In Aroclor by alkoxy groups substantially reduces the viscosity of the material. The 2-ethylhexyl ethers derived from Aroclor 1271 and 125; showed some promising properties as Industrial fluids. Because of the high chlorine content, the flash point of these ethers was very high (o30F). -it , E " ? f 5 Mono-2-ethyihexy1 ether ;f Aroclor 125^ represents a new type of dielectric, but pricewise, such cnloroethera c'ould never compete with Aroclors. The di-2-ethylhexyljeithqrs of Aroclor 1271 and 1268 are more symmetrical molecule^,and ;ntly have. poor, dielectric ii*Lz*esrdi*!: Iin*'TTaahb1lfe TIIT.. 7 * f f t properties. ' < . gDpiafcl td - aie* DSW 621489 rti STLCOPCB4095520 I #dOAh I1f$Mrss*'iV-St- ;* A . i / ::: 4t #,lt:i!%' ^ -<* 7` .ri^UdA. :i : tvi::fifffi v ~ i ;- t ':f-! f f ;:TI Sr .;. . ... : i New ethers'derived from highly chlorinated Aroclors are" readily 1prepared in high yield using procedures adapted ' from those specified for preparation of pentachlorophenyl ethers (R-4). Aroclor 1271 and 1270 give dlethers, while Aroclor 5^604 gives a mixture of di- and triethers. Mono ethers of Aroclors may be prepared in low conversion by using excess Aroclor. Ethers can be prepared from Aroclors and phenols and glycols other than 1,2-glycols; ethylene glycol gives hydrolysis only, and glycerol is unreactive. Dihydroxyoctachlorobiphenyl condenses with ethylene chlorohydi and with chloroacetates to give the corresponding ether alcohols and ether carboxylic acid derivatives. It is questionable whether the :an be pur,ifPiej d ^ ., o f iicient he good polymer intermed _ d . tf o se ethers derived from Aroclor show some rrorr.ise as tnctior.al fluids and dielectrics but have r.: i s ocir. ^ > V, ~ i vantages. DSW 621490 m fiRlff' f if i * dl H ' T ? f ?? 'T-T Jf STLCOPCB4095521 . * :l lue exploratory ..^2 and 3- ' * ` 4Ion -AroCELor chemist t > as suggested f5 Prepare ethers and thloethers derived from Aroclors and Ci2-Cl8 alcohols and me reaptans. Evaluate the thloethers as corrosion ^ijnhijbitors in oil and:gasoline. ; - ;; . ,. Reinvestigate the preparation of diallyl ether derived from Aroclor 1268 and 1270 using higher reaction temperature or the method with pyridine catalyst (R-S). React mercaptobenzothiazole with Aroclors using aimethylformaniae or dimethyl sulfoxide as solvent. Investigate the reaction between equal moles of Aroclor 1270 and sodium salts of bisphenol A or dihydroxyoctachlorobipheny1 using dimethyl sulfoxide as solvent. i * ^ * - ni INN 1 : i DSW 621491 si STLCOPCB4095522 4. * I , m * Ii s .. . ittmit ETHERS Ethers derived f rom*hexacnlorobenzene, the first type of compounds prepared" in 19^7 by the author as possible polyvinyl chloride plasticizers, were very incompatible. In 1953, some scouting experiments were made on preparing ethers from Aroclor 1270 using the excellent procedure given in R-4 for the preparation of pentachlorophenyl ethers. As expected, this procedure worked well for Aroclors giving di-ethers. The process consists of heating Aroclor and solid caustic at lScC with excess (50$) 2-ethylhexanol for k.5 hr, while the water is distilled off at the rate of formation. Etherification goes rapidly with little coloration. Water extracts the sodium chloride formed and excess NaOH used. No hydrolysis (caustic-solufcle material) of Aroclor 1271 `akes place at lcQC under conditions used in Expt. 1. The reaction mixture was neutralized in later experiments ' ore washing. This eliminates emulsion formation. ude bis (2-e thy 1 exy loxy )octacnl 3red lphenyl stilled over 1 h nr period to g! v<: 1 '6 g. .25-2 .mr.. w1 th out: indication of decompo: is tillate is a rather viscous, yellow, odorless aroclor l^oO, containing less reactive chlorine atoms, gave a mixture of mono- and diether at l60C (expt. 2). . A mixture of di- and tri-butoxyethyl ether is formed on neating A.oclor 5^60, caustic, and butyl cellosoive at O n : or hr. (Exp t. ^). studies were made on the etherifications of 71, 1260 and yhcC in Expt.,1-3.. Minor process variation should Increase the conversion.' (Expt. 3) Allyl alcohol failed to react at 110C with Aroclor 1271, most likely due to too low a reaction temperature (Expt. 6). This experiment, should be repeated u^ide? pressure allowing a , higher reactions tejnf>erature . A dlfal|yifefth4r of'Aroclof* may f be of Interest ilnside Monsanto, especially as a cross-linking agent for polymers.: * " * fc ir t PH DSW 621492 STLCOPCB4095523 equal s molest Of^fii-eiaylhexanol|and #|L&&f&inkh a? large | excess (5 OOJf) of "the Aroclor. Reac tl'wtwas^tiuiti slow,? 7 ; even at 2 JOC and over''a long Expt. A). ; **= The more highly chlorinated fraction|iih?Ai*bclor 1254 reacted first, as expected (Expt. 4). Although the mono-ether has a rather low pour point and fair dielectric properties, the process is expensive and gives low,, conversion. Preparation of aryl ether of Aroclor 1262 requires much longer reaction times and higher temperatures than for alkyl Aroclor ethers. This was shown in the only experiment tried (No. 5), where Aroclor 1262 reacted with excess m-cresol. The distilled reaction product was a mixture of mono-, dl-, and tri-ether. It is conceivable that more than 2 alkyl ether groups can be introduced since in the case of hexachlorobenzene up to 3 chlorine atoms were replaced by 2-ethylhexyloxy groups (R-9) (288805) No attempts were made to prepare methyl and ethyl ethers of Aroclors. According to R-U, hexachlorobenzene fails to form methyl and ethyl ethers. That this is the case for Aroclor 1271 has to be demonstrated by experiment. Rocklin (R-6) has an excellent method for the preparation of term achlorophenyl methyl ether using hexachlorobenzene, methanol and caustic in pyridine. It is conceivable that this method may work for the oreoaration of methyl or ethyl -` :,ers of Aroclor 1271, 1271,' 1268 and 5460. Ethers derived from unsaturated alcohols such as ally! and propargyl alcohol should also be prepared from Aroclors and r.exachlorobenzene by the Rocklin procedure. Unsaturated -thers are not mentioned in his paper (R-6). No ether alcohol Is formed on heating Aroclor 1271 with ethylene glycol and caustic (Expt. 8). Instead, hydrolvsIs (mono- and di-) takes place. This hydrolysis Initiated o_r studies on hydrolyzed Aroclor, now transferred to the Organic Cr.emical Division for development (R-7). The mechanism for tr.e unexpected behavior of ethylene glycol is not known. Glycerol failed to react wltn Aroclor 1268 at temperatures 5 | between^ 12_5jl7pCf ^Expt., %) . , Glycerol jis ijranlsgible with. ' Aroclor: which may account for this result. f Ncr common* * f solvent was found.for(this mixture. , * f L 4 ' DSW 621493 STLCOPCB4095524 jle experiment a. ed rroa for|2 -he,I WW* fmiJ fa: A 4: ^dichlorophenoxyjpentanol in J2.5jTc6nve Nm< yield (Expt. 10)'.~ This new ether alcohS fv ft melting_ (. -55C) A paairt of the 1,2,4-^161' fdroblnzerte (15 -TS^) hydrolyzed to 2,4-dichlorophenol. It is eoneeivabie that, 1,5-pentanediol will also react with Aroclor,1270. ,= Pyridine as a catalyst-solvent (R-6) should.beilnvestigated for this reaction. : Neopentyl alcohol and pentaerythrltol also should be tried with a model compound, 1,2,4-trichlorobenzene, and then with Aroclors . No thioethers derived from Aroclors were prepared. By analogy with hexachlorobenzene, syntheses from mercaptans should go smoothly. DERIVATIVES OF HYDROLYZED AROCLORS The most promising derivatives of hydrolyzed Aroclors are the bis-glycidyl ethers, on which most of our time was spent. This work is reported separately (R-8) . Bis-nydroxyethy 1 ether of Aroclor 1271 was prepared by condensation of hydrolyzed Aroclor with ethylene chlorohydrln. Reaction was rapid and quantitativ e (Expt. 11). This ether alcohol is very soluble in most or ganic solvents. The same general method was used to condens e hydrolyzed Aroclor 5460 (mixture of di- and trihydroxy) wi th ethylene chlorohydrln. No efforts were made to separate i somers. Our main object was to demonstrate a method to pre pare 8-hydroxyethyl ethers derived from various hydrolyzed A odors (Expts. 11 and 12). A possible use for aoether alcohol derived from Aroclors is as an Intermediate for polyesters and alkyd resins. For certain evaluation studies only di. -functional material should be used first; this will require e xtensive purification studies \rloxyl% desters Another seri es of Aroclor derivatives are the obtained in quantitative conversion by condensing|hydrolyzed Aroclor 1271 with ethyl chloroacetate. The product is very soluble in c ommon solvents and failed to crystallizej froiji several solv ents tried. The same difficulty wa'a observed ' . to recryqtall^z^. the*free acid:, ofc{^jfed|l|y$i|''I f. hydrolysis o f the corresponding ester. Nevertnelfssj^purlfication of such acids and alcohols should be* stud`i`ed' 4~ .. O' ur jrellmlnary s o 1 ub il i ty.^ s_tjidles were li il DSW 621494 CSJE?? ?_f- __%_?c *` STLCOPCB4095525 * ,, , , applications not re^u 0^:b*B>|^J.VQrd8.i These compound wi11|probably riot" be purcfeno' V* for!'*f f<ib4eVarn--p' ol*ymer" *"* ' 3 ' Aroclor derivatives are4'probably mixtures of isomers and their separation is a problem in itself (R-5) Low-chlorinated, monohydroxy Aroclor condensed with chloroacetic acid gives a product similar to 2,4-D, and should be tested for herbicidal activity. . . POLYURETHANES Hydrolyzed Aroclor 1270 reacts with diisocyanatodiphenylmethane to form a polyurethane. Since the starting material used was only partly difunctional, shown later by improved analytical procedures, the urethane formed is low in molecular weight. The value of this new urethane should be determined on a sample derived from d1-hyarolyzed Aroclor 1270 or 1268. NEW SOLVENT FOR AROCLOR 1270 Dimethyl sulfoxide is an excellent solvent for Aroclor 1270- It has the advantage over dimethylformamide of being stable to aqueous alkali; therefore, it should be evaluated as a solvent for reactions of Aroclor 1270 with sodium cyanide, sodium isethlonate and pentaervthrltol, all which ^re soluble in dimethyl sulfoxide (Exp t. lo). M U | if til if f!H ? t n Tlf T7 T* i STLCOPCB4095526 ,* ; , ''iVisi ,, 4 I _i ,, - i i i isralriiderlved fr^i|fct?b&j9Si?'/arel'very fheat stable and presumably flame-reCT#.t|u|^lwhlch' Suggests their "use as ^industrial fluids/ especially. where fire retarding 'properties are required'. * Data reported by St. Louis fare .given in Table I.. Viscosity properties are poor. longer alkyl gr^tiF?|"corfiBlTned with a lower Aroclor might overcome the viscosity deficiency. The evaluated ethers possess a very high fire point (625F); their flash points are between 510-560?. This early lead on Aroclor ethers as functional fluids led later to preparation of ethers possessing superior properties as functional fluids (R-9) Initial work Indicates low breakdown on heating at 550OF for 75 hrs. 45 Aroclor ethers were also screened as dielectrics. Data are summarized in Table II. Lot number K-779 and K-?30 are rather symmetrical molecules, consequently their dipole moments are low. The mono-2-ethylhexyl ether of Aroclor 125^ possesses superior dielectric properties (Lot number 15^51547) . The pour points of these two samples are 10C and 5C, respectively, which is rather high. These few experiments indicate that little chance exists t^ develop ar. ether from Aroclor possessing dielectric properties good enough to stand the substantially higher cost of the final product. T;.is work led to the preparation of o-chlorophenyl 2-tutox: ethyl ether possessing a pour point of -70C and a dielectr.c constant of 7-25 at 25C. Data on this and * other ethers derived from chlorobenzenes is the subject of a special report (R~9) . Monsanto has no purification procedure to eliminate all conducting Impurities. General routine biological toxicant evaluation at Creve Coeur of 4,41-bis-(2-ethylhexyloxy)octachlorobipheny1 (undistilled product, Expt. l) and 2-ethylhexyl ether of Aroclor 12cC (mixture of mono- .^iid dl-ether, Expt. 2) failed to reveal special activity. These two ethers were screened as CP Numbers 3075 and;8077 respectively. 5 'll Iff 1 11 H 11 M * s DSW 621496 STLCOPCB4095527 _A__P_P_A__R_A__T_U_S_ u i IIII; ? * 11 f 1 f ffs ,,.4..i.t.s.,. .,.._. 'i 'j } ' ji^ -j *'S" w i ;8 . All experiments were conducted vin'standard taper, Pyrex glass equipment. The flask was heated by means of a heating mantle. Oood stirring was applied to eliminate local overheating. For high vacuum distil lations a separately heated 10-inchtVigreux column was used. A Dean and Stark trap was used in the Expts. 1-10 to separate the water at the rate of formation. EXPERIMENTS 4 , '--Bis f 2-e thy ihexy loxy )oc tachlorobipheny 1 - Exp t. 1 ( 258306-8j This experiment was performed after successful preparation of di-2-ethyihexyl ether of hexachlorobenzene ( O 1 ). xture consisting of Aroclor 1271 (l mole, 499 g), hylhexanol (o moles, 780 g), NaOH (3 moles, 120 g as nd pellets), and 35 ml toluene was stirred at l60C 4.5 nr. The water was removed at the rate of formation. rification was rapid with litt le change in color. The :tion oroduct was treated with water to remove NaCl and ss NaOH. An emulsion appeared, but disappeared on ification. The dried reaction mixture was heated at C/0.3 mm to remove 421 g unreacted 2-ethylhexanol, I.5686. Conversion 75-9$. .: C, 47.82; H, 4.51; Cl, 41.07, 41.08. ;am;e (2C of this ether was distilled at 2p6-265C/ 25--'-5 mm to collect; (l) 170 g, bp 255-265, n5P 1.5576; (2) 38 g, bp 2oC-67C/G.5 mm, n2^ 1.5725; and (37 residue, 2.4 e. Duration of distillationuwas 1.5 hr with no indication of decomoosltion. Anal.; Calcd. MW 686; C, 29-00; H, 4.96; Cl, 41.45 Fract. 1. Found: C, 30-31; H, 5-52/ Cl, 38-17, v \ i % < ufl i: f M f Mil ' . . 1- > 7^ * - Some material was lost due to emulsion formation, accounting fort lower ^than expecd:ed,iorryersiorr valUe : f r, DSW 621497 STLCOPCB4095528 * &': 4' . lyinaocanoif (SpSpwyi ._... ,ijt 60 ml-tolUenefwasfstirred ai psollecting; ^diluted at 60 ml 100C of Water. tteL.-TMTM, With'400 ml '?of pfater^^et.. ^. ailze,dw^, sw.iith ^ 1.07 moles HC1 and washed at 80*100C (good layer separation). The excess alcohol was removed by steam distillation giving 430 g, r& ] ` * ` `` was stirred Conversion was 86.5#. This ether was treated wYth fine AI0O-5 at 120C, filtered and its resistivity was measured and found to be 1 x 1012 ohms-cm at 25C. Anal. Found: C, 55-54; H, 6.39; Cl, 29-83. These values indicate it is a mixture of mono and diether of Aroclor 1260. The product is considerably less viscous than Aroclor 1260. Butoxyethyl ether of Aroclor 5460 - Expt. 3 (328075-77) Aroclor 5460 (0.96 mole, 5^0 g) was dissolved in butyl cellosolve (8 moles, 944 g) at J0C, then 4 moles NaOH ____ flakes was added. A mild exothermic reaction increased the temperature up to 115C. The pot temperature was gradually increased from 1^0 up to l60C over 1.75 hr - while collecting 72 ml of water. The mixture was stirred for 4.S hr at loOC, cooled, and diluted with 900 ml of water. Acidification to a pH of 8 required 0.68 mole HC1. The organic layer was shaken with NaOH (10^); no hydrolyzed Aroclor was extracted. The final product was heated for 0.6 hr at 21CC/ 0.3 mm to give 740 g residue, 9656 conversion calculated as triether. )j Anal. Calcd . (C36H43.3CI6.44H13.5): C, 53-45; H, 4.38: Cl,29-08 Found: C, 53-63; H, 5-51; H, 5-51; Cl, 28.27, 28.31. i | The C, H, and Cl values check for the tri-ether. It is a viscous material and was not further investigated. i Mono 2-ethylhexyl ether of Aroclor 1254 4(303286,307297) Monoe triers of Aroclors are unsymmetrical molecules and therefore should be low melting and might find use as dielectrics and functional fluids. A mixture consisting of, Aroclor 1254 . i K5;moles, 1632.5 g), 2-ethylhexanol (1 mole,, 130 ,gj, fand one , IfnoSeiNaOH was hea*ted^ it 230?C for 2& hc,s ^Iftl'f |tHetvite$ fras* ( | I Colle--c<ted1 (13 ml) with 2-ethylhexanol, 'which was fre turned'. to the reaction mixture, li^tiijled |to igJ-vej|13g' The washed product iwjLs 7 unreac ied Atrpql-P* nfr*4ay *c* tionally DSW 621498 :WPlJiPPMJ ||i.P.J4||.ipi!).JJJk STLCOPCB4095529 225-40 241-45 245-40 - C -Tf pp 42.4 1 ll59l8'* 1^33 S, . 61.0 1.5788 v. 38.72 - - \ ,. > =. . 1; i a 84.3 1.5766 ^38.01 46.36, 50.53' 52.78 53-01 2 <78 i" , 3.87 4.63 4.70 Residue 33- Anal. Calcd. for C20H20CI5O: 39.1 52.8 4.42 'A / ft M Analysis values of fraction 3 and 4 check for a monoether. The residue (33 g) is a dark semisolid. Fractions 3 and 4 were screened as dielectrics (Table II). Cresyl ether of Aroclor 1262 - Expt. 5 (343706 gy L. Beck) A mixture consisting of Aroclor 12&2 (1.2 moles, 4b6 g), m-cresol (5 moles. 518 g), KOH (2.6 moles, 148 g), and 160 ml of toluene was heated under stirring. The water formed was removed at the rate of formatlon,collecting 60 ml while the mixture was heated at 17CC for 0 hr. Neutralization required 1.2 moles HC1 indicating a rather low conversion, therefore, the mixture was not worked up. The same fresh charge was heated at 200C for 12 hr in the presence.of,copper powder as qatalyst. After reaction,^400 ml of water was added and the mixture was neutralized ,witn*'0.25 mole HC1 and washed. Excess cresol was distilled off (208 g) and the residue was fractionally distilled at 1 mm. Frac t. 1 bp, C 170-200 Wt ,g ? 85 Anal. Found (#): c H Cl ' 48.45 2.25 2 200-240 - 1 .S |3 ' I ;24-280 I, f M ? H if I 4 ' | : 300-fI0: 208 ; 5302 lno| f 57.03 yy,if * f|62h6 2.95 2.97 , <, $. 4.14 Hi * Ms it *; W: DSW 621499 It . STLCOPCB4095530 I el ? prepare Tthe__^__l_a__l_l_ _ erheir of Arofljror 1271 ~h 1298305) A talxturefconsisting ot Aroclor 1271 It^mole, 250 g), ally! alcohol (4 moles, 240 g), and ml xylene was refluxed under stirring without dissolving MBpletely. To this was added 1.1 moles of NaOH and 2 g of -f i J|^d|:^-g>^|pbwder. and,, reflux continued,at 110C while collecting . skater. Apparently the 'temperature was too low; practically no reaction took place. The planned run in the bomb at higher temperature was never made. Attempts to react Aroclors with ethylene glycol - Expt. 7 ( 2b8b34 ~5) Arocloi1 1260 (1.5 moles, 552 g), ethylene glycol (10 moles, 620 g), NaOH (4 moles), and xylene (150 ml) was heated first at 130C, then up to l8oC for a total of six hr. The reaction mixture was neutralized using 1.03 moles of HC1, washed, and dried to give 500 g product. Anal. Found: c, 39-97; H, 2-32; Cl, 45.66; OH, 6-50.. Hydrolysis took place instead of ether formation. Aroclor ^xp t. 8 (2c^'Zl-2 ) mixture co.nsls- of Aroclor 1271 (0.5 mole, 24?.5 g), ethylene glycol (5.2 moi 248 g), ethylene glycol diethyl ether as solvent (700 g). an: 70 ml toluene was stirred at 150-27CC for 10 hr. Reaction product (206 g), mp. 220C, was identified later as crude hydrolyzed Aroclor 1271 formed in 59'.3# conversion. This ixrisuccessful ether synthesis opened up hydrolysis of mFociors (R-10) . :v ' ' ' Anal Calcd. 'or C12H2O2CI8: C, 31-20; H, 0.44; Cl, 6l.6 * : Found : C, 32.45; H, 1.32; Cl. 59-37. Attempted reaction between trlvcerol and Aroclor ii Expt. 9 (2oob42-3) ~ Aroclor 12o6 (1-33 moles, bCO g), glycerol (6 moles, 552 g), NaOH (3-1 moles), and 200 ml xylepe were stirred at 125-17CC over a 5 nr period collect!: %|total of 70 ml water. Material was washed and neutralized sQegive 4l g unreacted AArroocclor 12oS. From the wash waters aj^solated 20 g of product. .' ;r ' -lh Cjf, * i hi * if- * ? t tihp32*78| Hvl.33; C1,|62:12. Ii - J M ; . : .. Mi itifjiedL jp4ply.t Aro sH DSW 621500 STLCOPCB4095531 iti k f ........ *exaef __ _ ^ _ jjoncmmq 'to relnvestfgat# th^Jpre|^Jii|lJbr . :e tnilWieohorst _r,3^eSitanedioI' was| usea|?j^ ffindt Edli$UK& between r. ,thef OH groups changes the rate of|reaction, [hydrolysis Only occurred with 1,2-glycol)." 3.Of ~ l * ' Ifrl ' A mixture consisting of 1,2,4-trichlorobenzene (0.75 mole, 135.5 g), KOH (0.75 mole, 42 g), excess 1,5-pentanediol (6 indies, 624 g), and 125 ml toluene was stirred at 120C while collecting the water at the rate of formation. The pot temperature was increased gradually to 210C and kept 2 hr at this temperature. The salt formed was filtered off (4l g KCl) and the filtrate was neutralized with 0.114 mole HC1 and then extracted with ether. The ether solution was treated with caustic to extract 20 g of 2,4-dichlorophenol. The ether solution was distilled to recover 46 g (36^ of charge) of 1.2,4-trichlorobenzene and the fractions tabulated below. Fract. bp, C mm wt , nD" Anal. Found(^): C H Cl OH 1 140-130 is 18 1. ^*6^ 5 57.9 10.5 6.9 22.65 2 130-130 0.8 . 1C 1.4782 59-9 9-6 9. co 7.90 ^ 1 _ 1---- - 0 61 1 -5255 =4.3 6.1 25.8 6.82 4 22C-232 0.8 s 1.5281 35-4 6.2 23.9 4.57 Anal. Calcd. for ether alcohol: 53-0 5-6 28.5 6.83 t 5* ; * ; * f Analytical values for fraction 3 indica te that the desired 5-(2,4-dichlorophenoxy)pentanol was obtained in 32-5% conversion and 48.9% yield . < ft vM I Reaction between hydrolyzed Aroclors and ethylene chloronydrln n it t Hydrolyzed Aroclor 1270 - Expt. 11 (323953-4), { , Hydrolyzed Aroclor 1270 (0.242 mole. 111 ^ of partly dlhydroiyzed Aroclor, 6.16^ OH, calcd. 7-4C; was dissolved in NaOH (0.48o mole 2.5 N and stirred at 75C while ethylene chlorohydrin .(0-53 mole, 42.3 g) was added at once. The mixture was heated 1 upi to 90-S5C; the solution burned neutral|to icuienOlphthalein 1tIf# ' I- ! I - | ? i f ft i ill II iil i I * t f ;M DSW 621501 STLCOPCB4095532 `Confers lion: was' 92 t iJLi 4 & < v ft i :,: r 7* ^ ^4 -* f I l ' *^al. Calcd. MW 547.4; C, 55-90; H, 1.83; ;C|/|51-6j .OH,'35(22! i **#' - Pound: '- c,.?-*'3-6 .;'92; H, 2.71; Cl, 50.19;*, 50'l -83^|-6-$%, - $.6^4,># 6.A .7-. 3. The OH content of starting material was determined 2 years after Its preparation when the modified OH method was available. Hydrolyzed Aroclor 5460 - Expt. 12 (328995-6) The same general procedure as In the previous run was used. Hydrolyzed Aroclor 5460 (121.2 g of mixed dl- and trl-hydroxy cpd, 328966-7) was dissolved In NaOH (0.75 mole 2.5 N) and the ethylene chlorohydrln (1 mole 80.4 g) was added at once at 85C. After 20 more minutes t:. pH of the mixture turned to 8. It was heated for a total of 3 hr at 85-95C, and then washed until free of Ionic Cl, to give 132 g of a light powder. Conversion was 92-5% calculated as a mixture of di- and.tri-ether. Anal Calcd. tri-ether: C, 44.95; H, 3-04; Cl, 37-0; OH, 7-S3 Cl, 43.6; OH, 5.52 Found: C, 44.21; H, 2.6i; Cl, 42.38, 42.44; OH, 5-45, 5-i Reaction between ethyl chloroacetate and hydrolyzed Aroclors Hydrolyzed Aroclor 1271 - Expt. 15 (534605-8) Caustic (0.8 mole 32 g) was dissolved In QOC ml of absolute ethanol and hydrolyzed Aroclor 1271 (0.4 mole, 184.9 g, 7.605C OH) was added. Redistilled ethyl chloroacetate (0.88 mole, _ . 108 g) was added at once at 70C and the system was refluxed * for l4 hr; salt precipitation started after 0.5 hr and total salt formed was 48.2 g(0.84 mole). The ethanol was distilled off at reduced pressure. The semi-solid residue is very soluble in the low normal and branched alcohols and dioxane. No precipitation occurred from ethanol solution kept at -40OC over night. Precipitation using solvents such as pentane,. ether, water failed to yield a crystalline precipitate5; oniy : cils were formed. The crude ester was dissolved" In 300 ml of ethanol and refluxed 10 hr with NaOH (0.9 mole, 9 N). ; The ' : ethanol-water mixture (750 ml) was distilled off, the residue* diluted with 1000 ml of water, and refluxed. The water " * soluble material was filtered off .and the filtrate*, was act fled; t|o|y ife ldjf I62 |g' of' acid.1 f -- | If' \a DSW 621502 STLCOPCB4095533 Igent iised^Tbl analysis failed to dissolve tely . ; i tf'| ft | jaxnple N solvent was found Hopurity *the material by recrystallization vto; the point where it could be used as an intermediate for polyester type polymers. a Hydrolyzed Aroclor 1262 .- Expt. 14 (334617) A solution consisting of partially dihydrolyzed Aroclor 1262 (212 g, N 221, calcd. as diphenol 176-5, prepared in St. Louis Pilot Plar.t) was dissolved in 900 g ethanol containing 1.2 moles of NaOH and the system was refluxed. Ethyl chloroacetate (1-32 moles, l6o g) was added over a 68-min period and reflux was continued for 16 hr. Material was iso lated as in the previous experiment, thmheated up to 120C at 1 mm under good stirring to give 303 g product. Anal Found: A1.55# C, H. Product failed to dissolve in reagent used in the modified H-8-57- The values found indicate, as expected, a mixture of mono- and dieater. Infrared analysis, run as No. 5285, was inconclusive due to overlapping of bands for suspected functional groups. - Polyurethane derived from hydrolyzed Aroclor 1270 - Expt. 15 (318088T Equal moles of hydrolyzed Aroclor 1270 (0.015 mole, b.93 g, 316051, partly dihydrolyzed product) and diisocyar.atodlphenylmethane were stirred at 100-110C for 0.5 hr using 20 g xylene as solvent. Indications were of an . Incomplete reaction, therefore, 1 drop of N-methylmorpholine was added and stirring was continued for one hr at 120-30C. A solid precipitated on cooling, was filtered off and washed with ho: xylene to give 9-2 g residue (i). Precipitation of the filtrate gave a white powder, 0.6 g (il). Anal. Calcd. MW (711.7)*: c- a5-52; H, 1-97; Cl, 39-6;N, 3-9? Found: (I) C, 47-30; H, 2.48: Cl, 42-92; N, 3-57 (II) C, 43.89; H, 2.37; Cl, 37.18; N, 2.74 Starting -material was not completely difunctional (OH found , 6.l6^, calcd. 7.82#), therefore, only a low molecular weight ,, ' polymer could be formed. Product is free of phenolic groups. t :. ' t*ff t > t r* ^ DSW 621503 -V-- tf 1 T ^ vf 7 STLCOPCB4095534 11t- ... Aroclor____ Slat l;nsoluble^l3i*npatorganio|aol^enta.| Is faoon' as dimettiyl j-1 jsulffoxide (Die)fi^Majwouncedlalfampleii sfordered (January 1 |1955) from Stepan Chemical Company and found to be an excellent fsolvent for Aroclor. Furthermore, DMS is stable to caustic :and dissolves sodium cyanide, sodium isethionate and penta- jerythritol, all compounds slated for reaction with Aroclor 11270 when time allows. - STLCOPCB4095535 ' 1 sft->'' VIIIJ I? *3 PATENT * I- SITUAT ION :: -- ' J ' - i l it i; 'i , J-,| * ^ Eight patent disclosures were submitted as a result of this work on Aroclor Chemistry. * V D-1584 J. Dazzi - Preparation of ethers of chlorinated biphenyls and their uses as functional fluids, 6-3-54. : A' J. Dazzi - Ethers derived from chlorinated biphenyls as new dielectrics, 9"7-54- ' J. Dazzi - Dimethyl sulfoxide as a solvent for Aroclor 1270 and suggested uses, 3-8-55. J. Dazzi - New halogenated polyurethane derived from hydrolyzed Aroclor 1270, 7-18-55- J. Dazzi - New trlethers prepared from chlorinated terphenyl (Aroclor 5460), 12-1d~55- J. Dazzi - New synthesis of ether alcohols using 1,2,^-trlchlorobenzerc- and 1,5-pentanediol, 9-l4-56. ?g J. Dazzi - New acids derived from hydrolyzed Acoclors and chloroacet ic acid, 5-6- 58- * ** k ` J. Dazzi - New ether alcohols derived from hydrolyzed Aroclors and ethylene chloronydrin, 5-6-58. Disclosure D-I086 was filed in November 1955 as part of four patent applications on chloroethers as new dlelectricsjf see Dayton Cases 1658, I60O, 1662 and 1663. * ?' i i s{ More experimental data are needed in order to widen claims for submitted disclosures. , ' `' Him V l DSW 621505 STLCOPCB4095536 4 *i ipgm>- $r f-fv-f '< * ffy$- f t ff fggp^ l.1' Dazzi,' J^#*f!few epoiqr compounds derived fcrom^Aroi memo to thefldea Review Committee, dated 11-16-5* \k Dazzi, J. - New organic chlorine derivatives, memo to the Idea Review Committee, dated ^26-55 - Dazzi, J. - The Aroclors and other halogenated aromatics as chemical intermediates, memo to Dr. C. A. Hochwalt, 1-16-56 Part I; Tart II, 12-14-56; Part III, 11-7-57 P- B. Report No. 588 - I. G. Parben (Verdingen 1943) Preparation of pentachlorophenyl ethers. P. B. Report No. 589 - I. G. Parben (Verdingen 1943) Hydrolysis of decachlorobipheny1. Rocklin, A. L. - Substitution reactions of hexachlorobenzene. J. Org. Chan, 21_, 1478-80 (1956). _ Scnwendeman, Craver, Dazzi, LeBlanc, and Herbig, Synthesis and Application studies on Hydrolyzed Aroclors and Derivatives, RD-58-Pin. Rep. No. 1115. Dazzi, J., Exploratory Aroclor Chemistry. Part III. Glycidylation of Hydrolyzed Aroclors, RD-58-Int. Rep. No. II83. Dazzi, J., New Chloroaryl Ethers and other Exploratory ^ Investigations During 1953-1957, RD-58-Fin. Rep. Nof ll80. 10. Dazzi, J., Exploratory Aroclor Chemistry. Part II. Dlphenols by Hydrolysis. RD-58-Int. Rep. No. 1182. fMf * |iH * .- * * t mm* MI?. 9 | & f ? J % III *| DSW 621506 STLCOPCB4095537 STLCOPCB4095538 STLCOPCB4095539 >T 0 X I Oil T_T A NjDJH 4-H ' " M--- . :t am ^ ..... ^ O' v,'? f . .. JIWlNv "' "j No special toxicity tests were made on'compounds described in this report. A skin irritation was jfche consequence of the author's exposure over several^yiars gto^roclors, ^ octachloronaphthalene and their derivatives. ?.......... " f ' ? if l ' i if f ' if | f * i- (s ! !. I S. 5 DSW 621509 STLCOPCB4095540 YTI ff? i? - W I Carbon and hydrogen combustions were run at 800C. i | Nitrogen was determined by the Dumas method. . | , | - - ' > ' J- ' **'< -MM Chlorine analysis was run by C-35-55 method, which give# low values on compounds high In chlorine, such as the Aroclors 1268, 1270. 5^60 and their derivatives. The current modified H-8-57 Cl method was developed after the compounds described were prepared. For the OH determination in Expt. 10 the H-3-56 procedure was used. ':* t fi # | fMf flH ii * DSW 621510 STLCOPCB4095541 bt * '1 1* bH $1 r1 : nI :}f I< iu> li I f | ffl -* > i^i '* %^ i- i * i *> f$ * 1i r ii ill ; STLCOPCB4095542 \PPEW)fet A - NOTEBOOK REFERENCES* A 288806 288807 288808 288331 288832 28883^ 288835 288842 288843 2888^5 2583d 298 ?-C2 3983C3 303286 303287 310432 316088 328975 328976 328977 328983 328984 328995 328996 334605 33^606 334607 33^608 334608 334617 3^3706 343708 3^3713 f APPENDIX B - DETAILED LIST OF EXPERIMENTS %- ExDt. No. 2-Ethylhexyl ether of Aroclor 1271 (diether) J-Ethylhexyl ether of Aroclor.1260 (mixture of ?rf 'mono- and di-) * *' 4 ? A Butoxyethyl etner of Aroclor 5460 (mixture of dl * ' ' Jfrnd strl-) '' . ; *, c | | 5. I . * * e|he2. If 'Arofc|<ir|22||:^(|c^|-| f : | I H DSW 621512 STLCOPCB4095543 .sr*aci'< s Attempt! to^'eactlilr'oeioip 1260 wi| ycpi i 4 , . ifcta.-form an ether i 4 ' lr; 4 T ,* f % - ; , * . ' ' . ' Attempts to react Aroclor 1271 with ethylene glycol T' to form an ether 8f ' Attempt to react Aroclor 1268 with glycerol 9 Preparation of 5-(2,^-dichlorophenoxy)pentanol 10 Reaction Between Ethylene Chlorohydrln and Hydrolyzed Aroclors Hydrolyzed Aroclor1270 11 Hydrolyzed Aroclor5^60 12 Reaction Between Ethyl Chloroacetate and Hydrolyzed Aroclors Hydrolyzed Aroclor 1271 13 Hydrolyzed Aroclor1262 l^J Pclvurethar.e Derived Prom Hydrolvzed Aroclors 1270 Dimethyl Sulfoxide Solvent for Aroclor 1270 16 APPENDIX C - TABLES rcclcr Ethers as Functional Fluids lectr'c Properties of A oclor Ethers Table I Table II |i f fM M ? H y itX S' I ' | f 3- \ i | | | 5 H 4 i,. DSW 621513 I H `77 STLCOPCB4095544 "11 1 Jit liT^I i I t-rs # y AROCLOR ETHERS AS FUNCTIONAL FLUIDS" Lot No. Viscosity, cs., 210F 100F Viscosity Index Specific gravity 25/25C Flash point F Fire point F Four point F J-171^1 108.9 19200. *-f- 5- t* 1. J-171^, ^,b'-Bis(2-ethylhexyloxv)octachlorobiphenyl Expt. 1, ur.dlstllled. I, * | ^: < 3 fssNfe * a 2. J-1^15, 2-Ethylhexyloxytetrachlorobiphenyl, mixture as mono- and di-ether, Expt. 2, undistilled. 5. No breakdown of J-1715 at 350F for 75 hours. ; - J: i I As * f : ' -. Evaluated by Dr. R. E. Hatton, St. Louis and reported. a by memo to J. D., 5-12-5** i II I n i?411 111. *Hii?jt t *t i'it 1 ^ 11 ifffmM '! t DSW 621514 STLCOPCB4095545 M O n*.O Temp, C 100 - ^ * fl||nH 1 V !: i *'. - ? ' 60 cycles ' c 1 kc PF ,, * E>K PF 10 kc W '*1*221''iisfei -t .a 3-*U 3.43 .17 3.42' .06 25 5-85 2-5 3.89 1.02 3-77 4.9 -25 2.96 *3 2-92 1.2 2.91 1.1 -55 no data <n- kc DK PF 3.43 0 3.40 10 2 .89 0.7 f' V. Lot Number K-779 ICO 4.01 2-3 3.98 0.1 3-99 0.1 3.98 0 25 A.70 0.1 4.65 C.2 4.62 2.3 4 .20 14.4 K-780 -25 5.11 11.7 2.80 ^^ Q y 2.72 1.5 2.67 1.8 no data ICO ii .41 3.1 4.42 0.18 4.44 0.1 4.04 0 K-1546 25 - 5-22 0.6 .5-24 4- t ; . 0.15 5-24 1.4 5.16 9.8 ' : 100 A. 84 28.5 4.6 1.3 4.65 0.2 4.61 0 25 5 50 0.6 5.51 1.4 5-51 1.4 5.23 13-0 K-1547 lu 1) Lot No. K-779c4,|P-fJ|s(2-ethylhexyloxyJoctachlorobiphenyl, Expt. 1, undlstn|Ledfc| ^ 5 . <4 * * Its *Lot No. IT i ' ' v ft . i f > ? ! f j s ' DSW 621515 I* STLCOPCB4095546