Document X8Ymkra5jky7dLw1Kxyb046g

PLAINTIFF'S EXHIBIT API-100 the PENNSYLVANIA STATE COLLEGE 9 SCHOOL OF CHEMISTRY AND RHYSIC9 STATE COLLEGE, PA. AMERICAN PETROLEUM INSTITUTE RESEARCH PROJECT 42 THE SYNTHESIS AND PRttPSRTICS OF HIOHER HYDROCARBONS R. W. Schiessler, Director July 13, 1954 Dr. A. W. Horton The Kettering Laboratory University of Cincinnati Cincinnati 19, Ohio Dear Wes: In response to your letter of June 24, I am enclosing the synthetic details for the preparation of PSC 510 and PSC 174 1 am sorry for the delay, but we have been very busy and I am currently ill at home. As a consequence, I have not had an opportunity to look over the details for PSC 510 carefully, Mrs. Mills having extracted this for me from one of our theses. You will note that I have substituted the synthesis for PSC 174 (1-alpha-naphthyl pentadecane) for that of PSC 559, which you specifically requested. My reason is that the PSC 174 synthesis is more modern them that of PSC 559, and I believe it will give you better results. Of course, you can substitute the C^ nitrile, in order to get the Cgi hydrocarbon which you apparently desire. Instead of the high pressure technique reported with the PSC 174 details, you may prefer to operate at atmospheric pressure* If so, 1 refer you to our publication in the Journal of the American Chemical Society, 67. 206l (1945). ' If you have any further questions about these syntheses, please call on me. With best regards. Sincerely, Robert W. Schiessler Associate Professor of Chemistry P.S. My secretary will sign this for me in my absence. RWS The Pennsylvania State College has been renamed The Pennsylvania State University, and the School of Chemistry and Physics, the College of Chemistry and Physics SC-API-2565 I l , 4-n-Propylheptadecane this compound. same as that used la making 5-butylhexadecane, except that no attempt was made to isolate either the tertiary alcohol or the mixture of olefins* . ` . ' . n-Fropylmagneflium bromide was prepared by adding 6l5 grama (5 moles) of n~propyl bromide, in an equal volume of anhydrous ether, to 125 grama (5 moles) of magnesium. . 545 grams (2.25 moles) of methyl myristate, also in an equal volume of anhydrous ether, were then added to the Grignard reagent. , The complex was decomposed by pouring it into an ice-sulfuric acid mixture and the crude carbinol was isolated. This compound was dehydrated to the olefin mixture and the latter was hydrogenated to the corresponding paraffin. When the saturated hydrocarbon was being removed from the "bomb,; a' considerable amount of it was lost through .spilling* . *I 2. Distillation of 4~n-Propylheotadeeane Column: Hy-Vac . Fract. -- Time ~ Weight (gma.) 5:25 ----- n? ^ ----- Boiling Point (deg.C.) Press Still . Bottom Top of (mm.) Temp. of Col* Column (deg.C.)(deg.C.)(deg.C.J 111 0.95 .160. ' 138 120 1 2 3 '4 6:00 6:15 6:30 6:55 36 1.4333 123 43 1.4415 132 39.5 1.4423 134 54 1.4423 134 0.77 0.77 0.77 0.77 ? 134 177 131 154 157 150 152 134 143 . 142 141 In taking off cut 4* hot water had to be run- through the con- denser in order to liquefy a while solid which had collected. 5 ; 7:13 49 1.4423 134 0.77 135 6 7*30 44 . 1.4423 .134 , 0.77 189 152 153 142 142 7 7*50 50 .,144423 135 0.30 196 151 141 . . 3 . 3*50 39 1.4423 135 0.30 196 151 141 During the distillation on of the pot heaters burned out so that hear the end of the operation not enough heat could be obtained to get a small amount of material (about 20 gma.) out of the pot# All of the fractions were placed on a window sill where it was quite cold. White crystals began forming in a number of the bottles. It was concluded, therefore that' the white solid obtained in the taking off of fraction 4 was solid hydrocarbon. 3. Cuts 3# 4# 5, 6, 7, and 8 were combined and passed through silica gel* _The compound 'was labeled 4-propylheptadecane. . Yield was 43*5% based on methyl myristate* . Properties! . . Refractive Index! (n^) ..................................................................1*4423 . Viscosity at 20 deg. C........................................................................3.29 centistokes Density at 20 deg. C. ...........................^0.7943 grams per ml. " n-Tetradecvl Bromide C14-OH C, 4-Br ` . **'* , ' , 1 ft ' , n-Tetradeeyi bromide was "prepared"in the same manner as reported for n-decyl bromide. '.The synthesis was carried out on a very, large * Y* ?- V " n ; ^ - ' ' ' *T ' scale' by ithe 'authori fn 4945 for ,the:.work"repojrted in his Master's r- " r; >. ./ ' . I*."- i- ' Dissertation (3D ' - - . ' ' . - n-Tefcradecvl Cyanide ' . - C.i 4,--MBr --KCN--^r> ,,c j j.-CN... . '' ix two duplicate runs, 211 grams (3.2 g.-moles) of.93.5$ potassium cyanide were dissolved in 200.ml. of water and 2.7 liters- of 95% ethanol. After the addition of 386 grams (3.2 g.-moles) of pure-.x:-.-'.-'^ n-tetradecyl bromide' the solution was stirred for7 72 hours* An ;'r': :T'-.'additional 6? grams (1 g.-mole), of potassium syanida were added: and stirring continued for 96 hours. - 4. The two runs were combined and the majority of the solvent re moved by distillation at atmospheric pressure. The addition of 3 liters of water caused separation of two layers which were stirred at reflux for several hours to insure complete solution of inorganic material. The upper organic layer was separated and washed well with water, ether being required to avoid emulsion difficulties. The water layer and the water washes were combined,, ether extracted, and the solvent washed carefully with water. The ether solutions were combined, dried over anhydrous sodium sulphate, and the solvent re moved by distillation. The crude nitrile was Claisen-distilled at reduced pressure but bumping caused still liquid to be carried over with the distillate on several occasions. An attempt was made to fractionate the nitrile through Column A--5 at reduced pressure but no appreciable through-put could be obtained. After about 100 grams of low boiling material was separated the residue was charged to the Hy-Vacuum Column. . Fractionation Data Charge: 1250 grams/ofdrude;. n-t etradecyl cyanide Column: Hy-Vacuum Fctn. 1 2-4 5-1$ 19-20 * ,aT^mpr'ature ^C,-'' `Still Column;"" "^EvFti . V %** ' 'i46 140 146 150 160 134 130 105 93 .126 . 120 _ -105.. ..103 130 130 ; i 120 - '109- 140- - 13$' 120 V 117 14$ 146" -j' 122 - 116 y Press. JTotaB Wt. - mm'. -Hg `(grams f ` ,,, 0.3 - \ 0.7 0.6 - 15 62 114$ 1230 n20.5D 1.4402 1.4420 1.4425 1.442$. Residue: negligible  5. Fractions 5-1$ were of constant index and consisted of 1036 grains, a yieldjsf 76% based on n-tetradecyl bromide* Fractions ,2-4 and 19-20 are reasonable pure nitrile and if included in the yield would raise it to 84%* The 108 grams of lower boiling material obtained from Column A--5 which were not combined for the Hy-Vacuum fractionation had an index range of 1*437$ to 1*4417* The boiling point range is not significant as reflux was extremely3ow and variable. It is now :\ ; ' ' j -- evident that all of this- material should have been included in the Hy-Vacuum fractionation as probably a good percentage could have been obtained- as' pur.enitrile. 'i V-.'> ) r ..- The Synthesis of . , . r % * ", . 1(1-Naphthyl)pentadecane. PSC 174 n-Tetradecyl cyanide was added to 1-naphthyl magnesium bromide to yield^-tetradecyl-l-naphthyl ketone, which was reduced to 1(1- naphthyl)pentadecane by the Wolff-Kishner reaction* n-Tetradecvl-1-naphthyl Ketone -' The Grignard reagent of 1-bromonaphthalene was prepared from 122 grams (5*0 g*-atoms) of magnesium and 1035 grams (5*0 g*-moles) of the bromide at 20C* . To avoid precipitation of 1-naphthyl magnesium bromide it was necessary to prepare the Grignard reagent in 2500 ml. of anhydrous ether and 2500 ml* of distilled benzene and avoid cool-- ing the solution below 10-15C. ' - ." 6. After atirriag the reaction mixture for several hours, 1185 grams (5*3 g.-moles) of n-tetradecyl cyanide were added rapidly at 40C. and the reaction allowed to stir overnight at room temperature. Decomposition was effected with a slight excess of sulphuric acid mixed with crushed ice. the organic layer was washed with water and the solvent distilled. The residue was stirred with hot water (?5C.) for about an hour, the water was separated and the crude *' ; - tv ketone washed with dilute, .bicarbonate solution and then with water. the crude ketone was heated tinder water-vacuum to remove low boiling impurities and charged for fractionation.: ' ` : - Fraetionation Data ' Charges crude n-tetradecyl-l-naphthyl ketone . Column: Hy-Vacuua , Pressures 0.8 mm. : > *.../ '. ' Fctn* Still TemDerature C. Column B.Pt 1 2 3 4 5 6 7 8 9-20 21 22 23 251 251 255 255 252 252 252 241 246 260 321 330 360 233 . 233 233 233 '240 240 241 243 235 244 235 244 235 - 244 235 241 231 240 248 ` 241 240 252 251 300 260 277 211 211 . 210 217 215 215 215 213 213 217 217 217 223 ' 176 211 211 211 215 217 217 217 217 217 220 223 226 ' Total Wt (grams) 12 24 40 54 73 90 103 126 1099 1112 Residues, undetermined- 7. Fractions 6-20, although of constant boiling point, had a vis cosity rangS'from 10.49 to 10.69 cs. at 60C., the viscosity increasing with increasing weight-distilled. These fractions represent a yield of 6055 of fairly pure ketone from naphthyl bromide. Fractions 6-20 were combined, and a sample from the heart fraction reserved for physical property determination. l(l-Naphthvl)pentadecane: , The reduction of 215 grams (0.60 g.-mole) of n-tetradecyl-1- naphthyl ketone was performed in a 4000 ml. autoclave (hydrogenation bomb 2-B). After mixing the ketone with 260 grams (4*6 g.-moles) of sodium methylate, 60 grams (1.2 g_m.oles) of 100$ hydrazine hydrate 'and 1600 ml. of triethylene glycol, the mixture was heated to 200C. and shaken for eighteen hours. After cooling to 40C, the gaseous*^ reaction products were- allowed to escape, the material removed and V' =- : - v- the bomb washed with three 300 ml. portions of n-hexane and two 500 ml. portions of. warm vater*. v 'j- , * V .* - ; ^ *. * . - The Waiter wash solution'5,was "Warmed on %he steam-batfi, neutralized with dilute hydrochloric acid, and extracted with 300 ml. portions of hexane, adding the.extracts'to the original hexane wash solutions. The glycol solution was diluted with an equal volume of water and extracted with the original hexane solution. After further .` dilution and acidification (to eliminate emulsion formations) the. . aqueous glycol solution was extracted with fresh hexane. The various hexane extracts were combined. - V 4 3. Three additional reductions were carried out on a similar scale in the same manner as above, in each case employing the same ratio: of reactants and following the same procedure for treating the product. . The hexane extracts from the four runs were combined, washed well with water and concentrated by distillation. The residue, approximately 2 liters, was stirred at 65C. with 1500 ml. of 1:1 hydrochloric acid, the organic material separated and washed several times with water. The solvent was removed by distillation and the residue Claisen-distilled at 1-3 mm. About 770 grams (2.2$ g.-moles) of distilled hydrocarbon was obtained as constant boiling material from 923 gram3 (2.62 g.-moles) of ketone, a yield of 37$. A sample from one of the heart fractions had a .setting point of 41-42C. as compared with 39-40C. for the fractionated ketone. When equal volumes of the two materials?were .jmixed, .the .sample, melted at 30-33C. indicat ing that" the two materials were not~the:same. .The distilled hydrocarbon was combined and added to an ethereal solution of phenyl magnesium bromide (prepared frosi 0.3 g.-atoms of- magnesium and excess bromo- benzene) stirred overnight. Decomposition was effected with dilute hydrochloric acid. The organic layer was separated, washed with water, and the solvent removed by distillation. The residue was charged to the Hy-Vacuum Column and carefully fractionated. . Fractionation Data Charge: cruet 1( 1-naphthyl) pent adecane Column: Hy-Vacuum Fctn# Temperature C Press# still Column Q #Pt* (mm#Hg) 221 212 222 193 188" 0.3 1 219 210 222 193 190 2 221 208 212 189 190 3 225 214 216 191 191 4 223 213 219 193 192 5 221 212 219 192 192 6 221 210 219 192 192 7-9 220 210 223 194 193 10 220 210 225 194 194 11 221 212 223 200 201 0.5 -.12 221 210 224 198 202 13 14 15-17 18 221 222 219 220 211 224 212 225 197 222 206 . 214 196 198 191 189 198 198 198 198 0.4 19 230 217 219 196 197 20 232 218 221 196 197 21 232 219 221 197 198 22 - 235 222 222 197 198 23-28 boiling point increasing to 220 Residue: negligible 9. Total Wt# (grams)- . Average Eff.Time (60C.) 13 17 24 39 54 71 128 170 217 230 282 338 410 423 446 4l 518 568 s.Pt. 38-9 s.Pt. 40 s.Pt. 38-40 s.Pt. 41-2 s.Pt. 41-2 390*7 sec. 395.7 sec. 396.1 sec. 399.1 sec. .~ 397.6 sec. 398.8 sec. 404.1 sec. S*Pts depressed several degrees It will be seen that for the majority of the distillate, the boiling point is essentially constant if the pressure variation is considered# However, the efflux times tend to increase with increas ing material distilled# All the fractions had a light yellow color as a liquid but the solidified mass appeared white > 1. .10 When fraction 22, efflux time 404*1 seconds, was passed through a train of silica gel, the first fraction was colorless and had an efflux time of 387*3 seconds. Re-passage through fresh silica gel had no effect on the efflux time. Fraction 6 was treated in a similar manner obtaining an efflux time of 384*5 seconds. Fractions 10-22 (440 grams) were combined and passed through a train of silica gel. Fractions were taken, all of which had the same efflux time of 385*2-385*6 seconds. The recovery of pure hydro carbon was 90$. .) f v* */- '^ \