CONDENSATION OF TERTIARY Dl-METHYL AMYL CARBINOLS WITH BENZENE 1N THE PRESENCE OF ALUMINUM CHLORIDE Thesig for the Degree of M. 5. - John j. Sculati 1936 .‘rw-rrV'fiv-m xv '- n mrn~1vfi ' C34. 1.“); I. I m J4 .» -mfy J ‘3 I -1,m‘mv'L ALTYL CA??? TI? OL’ Jul 3&1»..— W'IWT PT‘T'MT“ It; 'T‘P’“ 4.1;. T2777“??? 07 ALT-"III“? OWL-1.77177? COFDEHSATION O? TTRMIAWV UI-IT7VVL ATVL CA?B-YJLS ‘VImv-:x«.~vvwv Ifi'vwvn .4 - ’J ”4‘ rfitSVIC? 09 ALUX NU? CVLJ“IWE Snkmittcd to the Faculty of Kichi- yen Sifts Collerc of Arricw1+nrc anfl Acvlied Science in partial fulfill- mcnf of the reonir ments for the raster of Science Derree. By John Jascpk Sculati June 1036 6\ \ i) \s Q» i\\‘ V V¢x \J‘i The author takos this op- portunity to acknovledwo his indebt- PanSS to Ur. R. C. "nsfon for bin friendly advice anfl helofwl succes- t10.9 durinr fhc Werformance of fkis work. 331663 HISTORICAL: This Faber deals Y"iih condensatiuns With elu- minum chloride. anerons conipnsa+ion reaciiono hava P‘f‘f‘n br3nr‘kt 311-3111" I)" SUP.“ TF’EJ'CTI ‘ ‘ nu“ . is as s Iikuric acid, thSQFUrons ooriovide, diln+€ or concffl+”9+¢‘ Fydvo- chlori¢ acid, ECFiiC an "Jo 9 acid, zinc CthTIdF, phasohorons Fusion eni Tric3rann ( dehydratinr P0+i3n of alwminwm n2 alcokols Lao arivf+ic cDMjonnds. fawn” +0 BC +*( orihnioal firodvni tvecn 1“9217371. alcohnl an? %Pn7€np invm hilariap. ”1?,nv 17 a u CL; .va 90..) + (Jill 6 It may he noted ‘Prn t? d a‘solnte alcohol, okon “(ntachloriflc eni ., 1016) first rvpvrféi "2*? in oonnr w o 3 ioricr 4 *iUTiC +k€ sromafic Vifi”ony1mpfhane r98 of tho reacfitn kr— iri ih? urn L ESFHOP ') 1 --+¢—+ ‘ .1: 1* r‘,'yi if '1 Lb 5C §V(LJ + L9» ’ {In— z*t if semi—molecnlrr I LNOHPLS 01 ihc fetciinr swhs‘ Hons zre word, ac)ut * . 1 ‘ . A " V: '-,r of akc yisii is diyhenglmcthanp e - . \‘-v V! fv TY 9-K , \ . ‘(l . ‘ (111K? :3qu 1"+.:3. ,._ )-'9~V61 , l.- in» CPSS (5:1) the yiplfl of diokcnvim 1' J-‘~ \ I} .L L; “(7‘ honznne siren? \ TF‘Flé, is D I": nfler Y‘" 4 S *7 C 5) 1'1 ~ use} in ex- rroatly .: . L1,:- .. r ~ g -» . 4 IA v . r. ' F -. ~ \ v r- - ‘\ - 5‘ s ”V . " crresed 'hereas tar iiell a seciniirr uro.ietc ix *. . 1* . .. .3 *1 ° - T . n- L:-'+€‘I 71,:3+ 3.“ \L-rl-‘t ."I‘Iptlu'idnrl L' Q ..:r._l. |._I} Pm. T“ n (I): f‘ 11 41" " r L - “‘- P‘t s' l ' ‘ a ‘. . 1 .J 10.9 A '9 '7 "9 101.) S’Ufi‘Cii 514.»; S"? 7 " c?" 3: LC alP’J“ hols conieuse vi‘L henzene accordine to the reaction: H506 H505 ‘C - HOH + 05 H6 —§1913+ ‘CH06H5. H20 R” R/’ with R beine a methyl, ethyl, or phenyl. When R is a phenyl group, the reaction is smoother and a larger yield of condensation product is obtained. Huston found that triohenyl carbinol will not condense with benzene to form the exoected tetra- phenyl methane. Rather, triphenyl methane is obtained. The reaction is: 1 1 (C6H5)3COH + 06H6 —rA C 3 : (06H5)3CH +. __ __ Seemingly, the oxygen is pulled out of the car- binol but what haopens to it is not known. Huston, Wilsey and Hradel found that diaryl- alkyl carbinols undergo dehydration rather than condensa- tion with benzene. (06H5)2 \ H506 \ c _ on *‘CeHe __§EE£1, c l CHCH3+.H20 // .Hsce H506 Later Huston and Maconber showed the same ef- fect in workinp with di-alkyl-aryl carbinols. H506 C2H5 H506 \ / A1017 \ c + 06H6 ———~—~e+ c = CHCHq-+H90 / \ / " " H509 OH H502 Huston and Sage“ (g. ég. Chem. soc., As, 1955, 1026) reported that the saturated aliohatic alco- hols (methyl, ethyl, prooyl, iso pronyl, butyl, iso- butyl, and iso amyl) do not condense with benzene. How- ever, they fonnd that unsaturated alcohol (allyl alco- hol) will condense With benzene. n. ' AlCl'! __ I: T 3' H20 == cstngon +-ch5 ~————~—. CH2 - clcsgcéLa..ngo With a slieht change in orocednre, huston and Fsieh (Doctor's thesis) were able to condense aliphatic al- cohols with benzene. It was found that orinary al- chole do not react at all: secondary alcohols react very sliehtly and tertiary alcohols react very readily to form the correspondinr alkyl benzene. H3» \ HSC\\ HeC’:; C - on +.C6H6.£191:s HFC-_ C - 06H5.lH20 H10 H30 / Huston and Fox (Master's thesis) condensed tart-butyl alcohol and tert-amyl alcohol with benzene to obtain tart-butyl benzene and tert-amyl benzene. Dimethylon butyl carbinol, dimethyl iso- butyl carbinol and dimethyl secondary butyl carbinol were successfully condensed with benzene to obtain the corresponding alkyl benzene (Huston and Finder.) The yield produced by eondensinn dimethyl tert-butyl car- binol with benzene was discourarine on the first run and no further cordensations were attenoted. 02 i ‘1‘ H 0 Q I I 1. Primary and secon“ary aromatic alcohols condensed with benzene in the oresence of aluminum chloride. 9. Mixed tertiary aliohatic-aromatic alcohols did not condense with henzene. Fehydration resulted. ?. Unsaturated orirary alcohols. with the double bond adjacent to the hydroxyl carbon,eondensed with benzene. 4. The orirary aliphatic alcohols did not condense with benzene: the secondary reacted only slightly, While the tertiary reacted readily. 5. Branchine of the tertiary aliohatic alcohols inhibited condensation with benzene. Es- pecially was this true as the hranchinp occurred near the tertiary group. EXPER IivTN’i‘ AL EATER ILLS Anyl bromide and secondary-amyl bromide and active amyl bromide were orenared by treatinc the respec- tive alcohols with bhosphorous tribromide. Phosphorous tribromide was obtained by treatine red phosphorous with bromine. Iso aryl bromide was obtained from the stock- room supply. Tertiary amyl chloride was orepared by treatinc the respective alcohols with concentrated hydrochloric acid. Acetone was C. P. grade. Magnesium (turnincs), esoecially oreoared for Grienard reactions, was used. The benzene was C. P. thiophene-free. The aluminumxhloride was a high grade commer- cial oroduct. Preparation of Carbinols Dimethyl n-amyl carbinol. From n-amyl bromide and acetone. Gripnard's reaction (Whitmore and Church) i. am. Chem. Soc., V. 55, pt. 1, p. 1561. 0 B. P. 65 to 66° / 15 mm. Aboroximate yield -- 40% Dimethyl isoamyl carbinol. From iso emyl bromide and acetone. Gripnard's reaction: B. P. 154° - 155° Compt. rendu 191?, 156, 1694. Aoproximate yield -- 15% Dimethyl active amyl carbinol. From active amyl bromide and acetone. Grie- nard's reaction. B. P. 150°; 640/ so mm. J. Bio. Chem, 1”?l, 91, 405. Dimethyl-secondary amyl carbinol. From secondary anyl bromide and acetone. Grie- nard's reaction. B. P. 150° — 1510 J. Clarke, J. Am. Chem. Soc.. 1911, 3?, 529. Yield -- 15% Dimethyl tert-amyl carbinol. From tert-amyl chloride and acetone. Gripnard's reaction. B. P. 150° — 151° Not found in literature. Yield -- about 5%. xo -CONDENSATIONS A. Dimethyl n-amyl carbinol, benzene and A1013. Trial I: Carbinol - 1 eq. - 32 pm. - 1/4 mol. Benzene - 5 eq. - 97 gm. - 5/4 mol. A1013 - g eq. - 17 gm. - 1/8 mol. A 500 ml. three-necked flask was orovided with a mechanical mercury-sealed stirrer, a dropoinp funnel and a condenser. A thermometer was introduced into the flask from the condenser and was suspended from the latter with a copper wire. A dryinp tube was placed at the top of the condenser. The benzene was introduced into the flask, and the stirrer started. The entire amount of A1013 was added to the benzene. The carbinol vas then added drop . by drop (about a drop every three seconds). This pro- cedure required about three hours. The temperzture was easily mai ntained below 30° C. and cooling with water was hardly necessary. The mixture was stirred for an ad- ditional two hours. During the addition of the carbinol, the mixture changed from a yellow to a dark red. All of the A1013 seemed to disappear but later a coapulate appeared which was dark brown in appearance. The mixture was allowed to stand for twentyfour hours: then decomposed with ice and hydrochloric a:cid. The benzene layer was separated and the acoueous portion extracted several times with ether. A little HCl was added in extracting with ether, to break no the water-ether emulsion that formed. The combined ether and benzene extracts were washed with dilute sodium.carbonate solution to remove any remaininp HCl. The mixture was dried and the ether distilled off. The following fractions were obtained from the residue at 15 mr.e 1. 40° - 120° - 4 pm. 2. 120° — 122° -1o pm. 3. Above 122° - 5 pm. The fraction boiling from 120° - 122° was di- methyl-n-amyl phenyl methane. Equation of the Reaction: CH1 ‘ L A1011 CH1CH‘CH?CHZCHQ 9 - OH -+C6H5 -'——-*—9 CH3 CH3 J I CH3 /2 Trial II: The sane procedure was followed as in Trial I. Carbinol - 1 eq. - 64 pm. -% mol. Benzene - eq. - 194 pm. —?% mol. A1013 - % eq. - 34 pm. - % mol. The following fractions were obtained at 15 mm.: 1. 40° - 120° - 7 2. 120° - 122° - 21 7. Above 122° - 10 Trial III: The same amounts and procedure were used as in Trial 1. The follovinp fractions were obtained at 15 mm.: 1. 40° - 120° - 4 2. 120° - 122° - 9 3. Above 1°20 - 5 Analysis of Fractions The fraction 40° - 190° / 15 mm. was found to contain a small amount of chloride. Further fractionation 0 yielded an unsaturated product between 40° - 49 . A satura- ted chloride was obtained between 49° - 5PO and is believed to be 2 chlor-P methyl heptane. /3 The fraction between 1°00 - 192° is dimethyl- n-amyl phenyl methane and its boiline point was found to be 249.50 at 740 mm. This compound was not recorded in v the literature. Carbon-Hydrogen Determination: Wt. Sample Wt. co9 % c Wt. H20 .1220 .4202 88.21 .1772 .1713 .5545 88.27 .1774 Calculated for Cl4H22 88,35 Molecular Weioht Deterrination: Wt. Samole Temp. Diff. Wt. Benzene .3401 .966 35.16 Calculated for ClAHpg % H 11.56 11.59 11.65 1." 7'3) 1 . Vf't o 185 190 Hf B. Direthyl isoemyl carbinol, benzene and A1017 Trial I: Carbinol - 1 es. - 3° rm. - l/d mol. Benzene 5 eq. - 97 pm. - 5/4 mol. AlCly - % eq. - 17 em. - 1/8 mol. The save procedure used in the previous con- densations was followe . The carbinol was slowly added to the suspension of A101.It in benzene while the tempera- o ture was kept between 95 and 30°. The orocedure took about three hours. Stirrine was continued for an addi- tional two hours. The mixture was allowed to s‘ani over nieht and was decomposed With HCl and ice water. Fractions at 15 mm.: ”)3 1. 40° _ 110° - pm. II. 110° - 114° - 6 gm. 111. Above 114° — 4 pm. Eflliiiflfl 23 Reaction: H30 H H CH3 Ngc - é - c - c - o - 0H +-c6H6 A101? 7 H H H CH3 CH3 H H CH3 RFC - t - c - c - t - c6115 +- H90 The fraction boilinr at 110 - 1140 was the condensation product dincthyl-iso-amyl ohenyl methane. Trial II. Carbinol - 1 eq. - 64 em. - % mol. Benzene - 5 eq. - 194 gm. - 2% mol. AlClz - % eq. - 34 pm. - % mol. The followinc fractions were obtained at 15 mm.: 1. 40°- 110o - 5 pm. II. 1100- 1140 - 11 pm. III. Above 114° - 7 gm. Trial III: 1/4 mol. Carbinol - 1 eq. - 32 em. 5/4 mol. Benzene - 5 eq. - 97 gm. AlCly - % eq. - 17 pm. - 1/8 mol. The followino fractions were obtained at 15 mm.: I. 40° - 110° - 5 pm. II. 110° - 114° - 7 pm. III. Above 1140 - 4 pm. Analysis of Fractions Refractionation of the fraction between 40° - 110° yielded a oroduct which condensed between 49° - 53°. It was saturated and contained a chloride and was believed to be 9 chlor, 9-5 di-methyl hexane. This compound is not recorded in the literature and no check was nade on the condensation oroduct. The fraction between 1100 - 114° contained the dimethyl iso amyl nhenyl methane and after re- peated refractiona’ion was found to boil at 233° at 740 mm. This compound is not recorded in the literae ./ ture. Carbon-Hydrogen Determination: Wt. Sample Wt. co? % c Wt. H20 % H2 .1825 .6132 88.24 .1260 11.57 .1818 .5882 88.25 .1872 11.55 Calculated for Cl4H9? 88.35- 11.65 Molecular Weirht Determination: Wt. Sample Temp. Diff. Wt. Benzene N01. Wt. .7994 0.691 35.16 183 CEJCHlBtEd for C14H22 190 C. Dimethyl Active Anwl Carbinol, Benzene, and A1011. TI‘lELl I: Carbinol - 1 eq. - 30 pm. - 1/4 mol. Benzene - 5 eq. - 97 cm. - 5/4 mol. A1011 - % eq. - 17 pm. - 1/8 mol. The same orocedure used in oreviows condensa- tions was followed. The carbinol was added to a suspen- sion of A1013 in benzene. The tenoerature mts kept between 75 - 50°. Addition of thr carbinol required three hourz. 531 gas was evolved freely. Qtirrino was con- tinued for two hours, and the mixture allowed to stand over night. It was decomposed and extracted. ins ex— tracts were fractionated. The following fractions were obtained at 15 mm.: I. 40 - 108° 5 gm. II. 108 - 111° 7 pm. III. Above 111° - 4 pm. The fraction boilinc at 10% — 111° contains the condensation product dimethyl active amyl phenyl methane. If ” Equation of reaction: H CH1 H Ch . ’ t. ' ‘ lCl ch - c - c - c — c - on ~P Cogs A 3.7 l H H H CH. H as. H CH.l ‘ ' ‘1 P.c - c - c - c - c - c635+-H20 F F H CH? Trial II: Cerbinol - 1 eq. - 32 pm. - 1/4 mol. Benzene - 5 eq. - 97 gm. - 5/4 mol. A1c13 - % eq. - 17 gm. — 1/8 mol. The followinr fractions were obtained at 15 mm.: 1. 4O - 108° - 5 gm. II. 108 - 111° - 6 pm. III. Above 111° - 4 pm. Analysis of Fractions. The fraction between 108 - 111° was refrac- tioneted several tines and yielded a orodnct which boiled at 109.90 at 15 mm. and at 290.5 at 740 mm. The product was the exnected di methyl active amyl phenyl methane. Carbon-Hydrogen Determination: Wt. Sample Wt C09 % C Wt. P60 .1615 .5999 88.70 .1601 .1827 .5911 88.?5 .1896 Calculated for C14Hn9 88.35 f. if - :20 11 0 11.71 11.61 11.65 D. Dimethyl secondary emyl cerbinol. hen7ene. end A1317. I H \ .tx Carbinol - 1 eq. - 7“ pm. mol. Benzene - 5 eq. - 97 em. - 5/4 mol. N'H AlClq - eq. - 17 p1. - 1/8 mol. The same procedure used in the breviins con- densatijne ”*s followed. The carbinol was slowly added ‘ y... to the stirred snsnension of A1017 in benzene vhile the tenneretnre res kent between 95 and 30°. The prodednre required eb\nt three horrs. Stirrinc was cantinned for an additional tvo hours. The mixtnre was allowed to stand over nirht, decomposed Vith ROI and ice water. Frictions et 15 mm.3 1. 40 - 111° - 2 II. 111 - 1140 - 3 III. Above 1140 - ? Cv3cvodvno‘p - u * so?” ‘ I CV1 Y H "oC HQC / '/ HqC - C - C - C- C- C U: +.nnO C a . F74 v——4 r. . 4 71 .‘ a 4"“ m1 1 . O I 0 “e fr'ctian bjzlir" .rt rem 111 - ll’ . ‘ . r s O a l.“ +. .’_ -"s "1Y-(spr‘lf-Iry4'wjri 1"" '3’:1;f\+ {~11 Y'l‘.('*f‘“"1 (:(‘f‘ )‘Y‘LT ‘1~~.v L‘rfivl “316171.71 310+1‘.’?1F o '1‘ A. d . re -- 1 _“ C~r31n 1 - 1 eq. - 65 :m. -« 31;. -., . r 1 D ,r e — , ec. - 10/ r". 9; r31. r I“! I 1 . w {11le — ‘1 PC. - 7" (9m. 1'; P.3—L. ”1162 f9710"‘inr‘ practifinss, were 311.5: ined. at a war 9 .. 1'1, .0 . . . . o “rfrecticnetivn of the ’rac*11nrvetreen f0 - lll ViFIAFi 3 3”?inct "hie? condensed between 55 — 590. It _ w ‘ _ I Q- : ' r fi ‘ : . ‘ I. _ was saturated en. c1nic1ned onlor:ne. It ‘0: believed :1 , Q n ‘ r, _ ‘l . "- A s 1'1. ': ‘ ‘ he 9 01 (r, “s? dl-fi€*:y‘ 'exiur. T-Ic co;;uun~ 15 but r‘3117e112' ti;)n nr'1.1H1t. Tie frrc+ivn krtvrcn 111 - 1140 cent inn” +15 'iinrfifl *1 SFY‘DWiFTV'?“T'1 rhr if] wetivnqe 51*? e’ter‘irefrec- . . ‘ - - e 3 t13net11n11r1s f‘rnm. +3 exneeted censtrrts 9 .. J - ' slifibt imgiritirs. "Bis cemjoini is rut +ne litere‘rre. 3ar11u—"vdr1rrn betrrwiheti ns: "77‘. 71.11-11]; "ft. CW} [3 C ‘1" . 7:0.) ,1cnv .srgl 3~.o" .17A1 .w. 1,. Celculet:l for C .VGO 22 MV’. - tir- O I and In View Drum +1. A ' - H) :7? ’Lii.‘ (\AVV';' 1 .‘V‘ J‘ '4‘ j ‘1‘ I J ‘0 1‘ C‘ Li.J" ' 1" 11.31 :‘F 110K.) ne‘w' we; ., J1.. I‘J. '1" 3. 4‘4. AIL m ‘.. L rlr: 11,3 frrctiw The mix 1" T‘ F "1. *5 .,. nege ‘ Y) g“rh?1101, tert. er'l P II: rhinol - 1 eq. — Vex: ~ 5 6g. ~ f‘ ,7 - 71, 6:10 '- 'e 551*}; prjced‘fl‘e‘ '71-, V. . F133. A"! 17 Pm. FIE. 1P‘I Red in ”EK‘ ”5T1” 133 31". '30 Al etrep“ “5 ‘ r' J‘JJ.“‘ 4'1“!“ Y‘ . ~ _ hm.11 I) ”AC; A 5 - .1 'IT 3 '2‘ 1? ,. 3 f 1 "'. 1 3" W, . l \ 1F, ’ -1't ‘g—L .' I ‘1’ IT: ) .L o /-'3 . ll {-3 1") 1- . f‘np fiver]; 1.1;: 111') ._ "="1 ‘ 91.3 .‘V‘ :, 1.-...- V Vi'z LYI .;(.i'-2’1€‘ 7A0 "'9‘, u . . 11L ‘W . . 1.. ,.- ‘ .tirr.h. 'cs The nixtwre hydral?ze4 W and the T69 ct vs: ht ..~. - -. RWJUnt 1*? a e N soilinr 23 1‘- u‘ w ‘ .L" I" v. H ‘C oro- P’T‘I’ln fivft‘rf'! n] gt.) Q C it» 1P2“ CT 3(37104’; o Determinati3n of ?h*siccl Cfiretents. \I -- ‘. ‘ ‘ r‘ . " r ‘: “ (V - ”. ’y‘a ‘ ‘0‘ , r 1‘ Dene. ty mete-1.1nc1t1 Ins < e de ('11.; o. with the Abbe refractomecer. teneierrtcr‘rz;"" iL~ Ffiu"'uue' dr‘.ww' i” ‘ 'rthi” Tre DnHony tensiometer elves e ‘iel reedan V‘ici r“st he “‘Iltin‘ieq ”V *“e °+'nderi 7’ th* (coaret: ‘ in error to ob‘ in fur rnrP ce tension. ”31‘ the 1J‘)p-vw‘ifihi ineti r‘, t‘r <77r?ecr‘ tr:- F" .3 H. ’3 "r‘ h.) a I ll .34 3 7’ 1r 1 J r " 7 7 AFF .- .. , n . u - ficSS '1 rlch (/A: 1 frectiun 3f icezl drav" h“ / w a” ’ fé 1.") "1'? otfin'rvcwi ”c*"chrn‘ ‘zr calmnwlciewi by th: ferrule: 73 _/7 ‘r/? z 5" ' 1Y1 itiir- : j“ , -ezn c: 1r 1? (vinrDOIUId 1. BULK“ E?‘ 1"eirht d . dC‘n3i+3r 7/ surface tension The Ohsirvci malecn‘1r ”llUPP *as (.1Chlated 1‘1? ‘4“! its density. by the formula: T rm T1 Ialecnler refrections flrmule: i n 1"}? ‘1 eh I” d n mheareticel dividinr the malecnler veivht of +he roinres : 16.n7 " : nnxher of cerhjn atoms tLe ted TV L were celche I 4 I77 L+ 2' : molecular refractior refrrctien molecular refrzc were f *ians H~.mm oa.mm Hm.mm mm.mm cases om: mm.mm mm.mm mm.mm .ono Ommd.H mmm:.a Hmm2.H a can macapomnmmm amazomaoz one seapowhwom mo NmUGH mmo m memo . o . oemmo mmo mmo mmo m m mmmo u o n o u o : memo mmo m mmo mmo mmmouomAmmovmomAmmov mmo mmo ammo u oaammo: mmo ooflflpwpfim Mi C”La9 1:! F" «a i 21 -C‘ 7 I. ‘ , ,~.‘ - 1 a .' v9 Iniex 01 2e 1.c*11n (n1 -jleeiic. Refrec‘1:v4. f: r , j A I ~\ h, . 9" A: h (gee fuel: on IIrCedin- )eFF.) Tith the exceetion of the fourth comvénnd v be noticed t*et tie index 3f refrzct ed a? the enrvcene were lerpei , ~*--P~ v-‘r v" -1 ~ -0 ”'1" .“ “ '7 “ I. " :et c11,11u1 v1. crcer11ng,r dudl+ n1 mn1 ref STFfériFd. V)W€V€“, 1+ K's 1“Pen H *10;. *‘gt refrec+ion increrze '1 3n ‘0 ediacent czrh1n EtOI‘ . W“ iecreese T Ch 3 -. ' ‘ r ‘ .r ’ I \.‘ 5‘ ' ;‘ H .‘N ', ‘1‘ 1“ '1 01+ tr1t )n {runnernt cm. can .tLL 9. 1' h. '1133 as 1: eru'n on tee table. 1.9 mm.:am mm.-m ma.~am m~.mam ocdoh s> m~.omm mn.cmm m~.omm m~.omm .ono misHo> HwHSUQHOS 0cm Hmww domnm majww mijw lell CON 6 NHHIHHH m.ooa HHH-OHH OHIONH .88 ma o.mmm m.omm o.mmm om.mzm .es OJN .m .m mmo m m mmmo-ououommmo m mmo mmo mmo mmmo u omAmmovmomAmmov mmo mmo mmoo u o Hammouc mmo mommpmnzm .mmfipfimcmo .mucflom wcHHfiom Boiling Points, Densities and Kolecular Volumes (See table of computation on precedina page.) The difference between the calculated and found molecular volume was probably due to chain branching. The formula for calculatinv Vm held only for straight chain compounds, so that the calculated value would he, in this case, that of n-octyl benzene. It Will be noticed that tte Vm increased as the euroeens were heaped except in the case of the di-metbyl secondary amyl phenyl methane where the Vm decreased. This may be due to the heaping of eurogens on adjacent carbon atoms. Kauffmann states that a decrease of molecular volume is effected by the heapinp of eur0pens on adja- cent carbon atoms. This accounts for the difference between the calculated and found molecular volume and also explains the decrease of the molecular volume as noticed in the case of dimethyl secondary-amyl ohenyl methane. Kauffmann noes on to say that heaoinp of euro- gens on other than adjacent carbon atoms increases the molecular volume and decreases the boiling point. The experimental evidence above entirely agrees with this statement. The molecular volumes of di-methyl n- amyl phenyl mettane, dimethyl iso amyl ohenyl methane and dimethyl active amyl phenyl methane gradually increased while their boiliny points decreased. It would be exoected that the boiling point of di methyl secondary amyl phenyl methane would be hieher than the others since it has a greater density. This did not hold in all cases as the di- methyl n-amyl phenyl methane was found to boil hiaher but this may be due to the impurity of the dimethyl secondary amyl phenyl methane. 3.2 s.mam :.mam 1.0Hm .ono m.mam w.mam m.mam ~.mam hsozso whonownwm o.~m: m.mom m.mom .uslacnm mmo m mm.mm sm.mm mmmo u o 1m cnmuo mmo mo ms m m m Ho.Hm ww.wm mmo . o u o u ommmo mmo m was man afl.am as.am memo . o mAmaov omAmmov mmo m mmo ma.mm mm.mm mmmo u o Hammoa mmo >5025n .psuqonm nofimcca mommusm mocmpmpdm mnonomumm cam cofimcea oomwanm Surface Tension and Parachors (See table on preceding pane.) The parachors were calculated by using the atomic and structural constants of Mhmford and Phil- lips (g. Chem. Soc. 1929 — 2112), These constants were: C 9.2 H 15.4 Double bond 19.0 6 memb. ring 0.8 Chain branching .3 Branching on phenyl ring —6 The surface tension values determined by the drop-weight differed from those determined by the Du- Nuoy method. The parachors, as a result, also differed. The parachor, as determined by the DuNuoy method, check with the parachors as calculated using the values of Mumford and Phillips. A new set of constants must be calculated for the drop-weight method in order that the two methods agree on this series of compounds. 34. Summary: -- l. The tertiary di methyl amyl carbinols (n-amyl, iso amyl, active amyl and secondary amyl) were condensed with benzene in the presence of alu- minum chloride. 2. The di methyl tert-amyl carbinol showed little tendence to condense with benzene in the presence of aluminum chloride. 3. The branched chain carbinols showed decreasing readiness to condense with the benzene as the branching aporoached the carbinol group. 4. The physical constants, such as boil- ing points, densities, indices of refraction, molecu- lar refractions, molecular volumes, surface tension, and parachors, were determined for each compound. 5. The relation between structure and physical properties was shown. v.1.A‘3‘I‘tllxlo I . . . .. .. . . . .f to): .0 ‘1.“ ...‘ooe.(£ \{toi§.“t1’0l.,l .130...) 1.111- .... x.‘ . p. . . . . I. ~ n.01Ily . . . 4 V .0,»n . Kiwi .0..u.fl ‘ 1: .l.... .. _ .,..... M I I. nu...” ' 0’: qr“.vl.ltl.h;,.uuln. .. .| In. I! . . . ‘7 . , . . . . .l . . 1..) (Ink. by»- . . .v , . . Wm- \ r- H Li. an. v: