i1;:32:22?2;:2:32:12: ‘x : 7 w 1 1.. 5.135 . ,‘ \‘ l . .‘- ‘ '1 '3 "1 f“ L"! k. (j I «- \ L4,. v I'\ k- . K I pm. CUflbLNSAIlUN 0F TLHTIARY ALIPHATIC CAnBlNULS MITH ABOfiATIC COMPOUNDS IN Thb thSbNCL 0F ALUMINUM CHLOfiILb UCTYL ALCOHULS AND BLNZQNE Thesis for the Degree of M.S. Michigan state College B. Robert Breining 1938 CONDnNSnTION OF TLnlInnY ALIPHATIC CnflbINULS WITH AMOMAIIC CUhPOUNDd IN Tfim PMESLNCL OF ALUMINUM CALOKILE UCTYL hLCUhOLb AND BbNZmNE A Thesis submitted to the Faculty of Michigan State College of Agriculture and Applied Science in partial fulfillment of the re— quirements for the Master of Science Degree By E. Robert Breining {arch 1938 ACKNUELLLGLMLNT The author takes this opportunity to acknowledge his indebtedness to Dr. R.C. Huston for his friendly advice and helpful suggestions during the performance of this work. 33 16 12. CONTQNTo HISTORICAL Condensations Summary Other Methods for Preparing Alkyl Benzenes LXPLRIMLNTAL Material Preparation of Grignards Preparation of Octyl Alcohols Condensations General procedure Di~ethyl n-propyl carbinol, benzene and aluminum chloride. Di—ethyl iso—propyl carbinol, benzene and aluminum chloride. THEORdTICAL Theory of Condensations Determination of Physical Constants Boiling Points, Density and Molecular Volumes Index of Refraction and Molecular Refractions Surface Tension and Parachors l4 CUFTnNTS (continued) Page sUn my 29 BIBLIOGfiAPr‘ HISTOHILAL Condensations A history of condensation reactions brought about by such catalysts as sulfuric acid (1), zinc chloride (S), phosphoroic anhydride (3), phosphoric acid, phosphorous pentachloride, acetic acid (4), sulfuric and acetic acid mixture (5), magnesium chloride (6), stannic chloride (7), hydrochloric acid (8) and aluminum chloride (9) have been covered by former workers in this labora— tory. However it was felt necessary to include a brief summary of research work carried out in this laboratory involving the reactions between alcohols and benzene in the presence of aluminum chloride as a catalytic agent. The first work in this field ves stated by Huston and Friedemann (10) who found out that primary aromatic alcohols react with benzene in the presence of aluminum chloride. Penzyl alcohol reacted with benzene to give di-phenyl methane according to the equation: ‘ul c N \J 1'? . A ’7 " "' ' " When equimolecular amounts of the reacting substances are used the yields of di-phenyl methane are not large (about 50$) and the yields of secondary products p-o-di—benzyl benzene, anthracene and tar are quite large. If an excess of benzene (5 moles) is used the yield of diphenyl methane is increased, the yield of the secondary products is decreased. Later Huston and Friedemann (11) showed that secondary aromatic alcohols condense with benzene under the dehyd— rating influence of anhydrous aluminum chloride according to the general equation: 1 "u -LAl-C1gl_s 06a - c - Cefis + sac H . c.- CIJ- Ori + Ceh R C she“ 6 LU -- When R is the phenyl group the reaction is smoother and a larger yield of condensation product is obtained than when R is a methyl of ethyl group. The ethyl group has a greater retarding effect than the methyl group. An excess of aluminum chloride tends to eliminate a phenyl or an alkyl radical from the product especially if the temperature is not kept low. Huston (12) found that triphenyl carbinol did not condense with benzene to form tetra—phenyl methane as expected, instead the product formed was tri-phenyl methane which can be expressed’by the equation: (C61'I5)3C0fl + CGHS =£Al_Clg)—9 (CeHJE‘)ET-I + _________ Apparently, the oxygen is removed from the carbinol and its . ‘IIII'II. III; I 'Illllfl...‘ its disappearance or migration has not been determined. Huston and Sager (15) reported that saturated aliphatic alcohols (methyl, ethyl, propyl, iso-propyl, butyl, iso- butyl, amyl, iso-amyl) do not condense with benzene. Unsaturated allyl alcohol condenses with benzene according to the equation: H2C=CHCHEOH . 0636£Alfilglscazcecagcaes + ago The yield of the allyl benzene was 16%. Huston and Sagar reported in the same journal that of the alcoholic derivatives of aromatic hydrocarbons, only those in which the hydroxyl group is on the carbon adjacent to the ring condense with benzene in the presence of anydrous aluminum chloride. Unsaturation on the carbon adjacent to the hydroxyl group increases the reactivity of the hydroxyl group toward the dehydrating effect of aluminum chloride. Huston and Goodemoot (l4) condensed cyclo alkyl carbinols with benzene in the presence of aluminum chloride and found a progressive increase in activity as the number of carbon atoms of the ring is reduced from six to four. Huston, wilsey, and Hradel (15) found that di-aryl alkyi~ carbinols do not condense with benzene in the presence of a luminum chloride, instead dehydration occurs, as expressed by the equation: b t z. 0-011 + CGEES _£&l-Clgl,n‘ 5;c_cace3 + H2583 CLHS‘ K’6fi5 Later Huston and Macomber (16) showed the same effect in working with dialkyl aryl carbinols: C H.— 051 _ C h .6 D\C’ “15 + C H -Lflil}. 6 5‘ C-Chc1zs 4, H 10 - ., \ ; 6 6 "‘ :‘ I Le) Id Grit. OH L -1 a a 2 5 Huston and Hsieh (17) with slight modifications in the normal procedure for condensations were able to condense alephatic alcohols with benzene and benzene derivatives. Huston and Fox (18) condensed tertiary butyl alcohol, tertiary amyl alcohol, dimethyl n—propyl carbinol and dimethyl iso—propyl carbinol with benzene to form tertiary butyl benzene, tertiary amyl benzene, dimethyl n~propyl phenyl methan and dimethyl iso-propyl phenyl methane in good yields. Huston and Hinder (19) condensed dimethyl n-butyl carbinol, dimethyl iso-butyl carbinol, dimethyl secondary butyl carbinol, methyl ethyl n-propyl carbinol, methyl ethyl iso- propyl carbinol and tri—ethyl carbinol with benzene to obtain in good yield di—methyl normal butyl phenyl methane, di—methyl iso-butyl phenyl methane, di—methyl secondary butyl phenyl methane, methyl ethyl n-propyl phenyl methane, ()1 methyl ethyl iso-propyl phenyl methane and tri-ethyl 'phenyl methane. Huston and Sculati (BO) condensed dimethyl amyl carbinols (n—amyl, iso-anyl, active amyl and secondary amyl) with benzene in the presence of aluminum chloride to form the alkyl benzene and also found that the branched chain carbinols showed decreasing readiness to condense with benzene as the branching approached the carbinol group.' Eranching of the tertiary aliphatic atoms inhibited con- densation with benzene especially if the branching occurred near the tertiary group. <::~ Summary 1. Primary aliphatic alcohols do not condense with benzene in the presence of aluminum chloride under the given ex- perimental conditions. 2. Secondary and tertiary aliphatic alcohols condense with benzene in the presence of aluminum chloride to give the corres ending alkyl benzene. The tertiary alcohols reach more readily and five higher yields of the alkyl benzene than the secondary alcohols. 3. Primary and secondary aromatic alcohols condense with benzene in the presence of aluminum chloride to form benzene derivatives. Tertiary aromatic alcohols do not condense with benzene. 4. Mixed tertiary aliphatic—aromatic alcohols do not condense but the dehydration occurs. 5. Unsaturated primary alcohols with the double bond adjacent to the carbon containing the hydroxyl group condense with benzene. 6. Branching of the tertiary aliphatic atoms inhibit condensation with benzene, particularly if the branch— ing occurred near the tertiary group. other Methods of Preparing Alkyl Benzenes There are many ways of preparing alkyl benzenes recorded in literature. The polymerization of alkyl acetylenes (al), the reduction of phenols or ketones by zinc oust (2a), the use of zinc alkyls and benzyl chlorides (£3), and the dry distillation of an aromatic acid with soda lime (24) have been successfully used. The most frequently used methods are the Fittig Synthesis q discovered in 1934 (25) and the Frieoel and Craft re— ‘ ;ction discovered in 1877 (36). The Gringnard reaction can be frequently employed as in the preparation of normal propyl benzene from the reaction of benzyl magnesium chloride and di—ethyl sulfate (27). filkyene benzene derivative prepared from Grignares can be reduced to alkyl benzenes (28). 13}.me Iran}; EAL Materials n—Butyric Acid This substance was obtained from the store room; having a boiling point of 162° to 185? C. iso-Butyric acid C.P. iso-Butyric acid was obtained from the Central Scientific Co. at Chicago, Ill. Boiling point - 151.53 to 154“ C. n-Butyryl Chloride was repared by the reaction of ’U’ phosphorous tri—chloride on buyric acid (29) accord— ing to the ecuation: :cxzcabcazcuos + PCLE __- 3CHfiCHECHECOCL + P(0H),~ A L . . . . o 0 Belling P01nt 100 to 101 C. iso—Butyryl Chloride was prepared from iso-Butyric acid and phosphorous tri-chloride. Boiling point 0 o 90 to 91 C. Ethyl bromide (C.P.) was obtained from the store room and was a product of the Eastman Kodak Co., Rochester, O N.Y. Boiling point 38.0 0 Magnesium. Fresh Magnesium turnings were obtained from the store room and allowed to remain in a vacum dessicator, using CaClV as the dehydrating agent, C. until ready for use. 7. Anhydrous diethyl ether (C.P.) was obtained from the store room and was allowed to stand over sodium, and as it was needed the ether was distilled on a water bath. Boiling Point 34.50 C. 8. Ethyl Magnesium Bromide was prepared as described under Grignard Reagents. 9. Diethyl n~pr0pyl carbinol was prepared by hydrolyz- ing the product formed when two moles of ethyl magnesium bromide reacted with one mole of butyryl chloride. 10. Diethyl iso-propyl carbinol was prepared by hydrolyz- ing the product formed from the interaction of one mole of iso—butyryl chloride and two moles of ethyl magnesium bromide. 11. Benzene (C.P.) trio-phene—free was obtained from the store room and allowed to stand over sodium and be- fore using the benzene was distilled from a Wurtz flask on a water bath. Boiling point. 79.6° C. 12. Anhydrous aluminum chloride (tech.) was obtained from the store room. Preparation of Grignard Reagent (30) In a three liter three —necked flask fitted with an efficient stirrer, refluv condenser and dropping funnel is placed four moles (98 grams) of fresh Nagnesium turnings. Thirty ml. of a mixture of four moles of the halide and 500 m1. of dry anhydrous ether is added directly to the dry magnesium. After the reaction has started and pro- gressed a few minutes, 200 ml. of dry ether is added directly to the reaction flask or mixture. 475 ml. of the above halide—ether solution is placed in a separatory funnel and added with stirring at the rate of one drop per second or less. The remainder of the ether-halide solution is diluted with 300 m1. of ether and added at the same rate. The mixture is allowed to reflux during the addition with no external cooling being applied. After all the ethereal-halide solution is added the stirring is continued for four hours and allowed to stand over night. Preparation of Octyl Alcohols (31) In general the preparation of the tertiary alcohols, di-ethyl n-propyl carbinol (Z—ethyl hexanol-E) and di- ethyl iso-propyl carbinol (2—methyl-E-ethyl pentanol—3) moles of ethyl magnesium bromide with two moles of the proper acid-chloride in ether solution or in other words, two moles of ethyl magnesium bromide with one mole of the proper acid chloride in ether solution. Two moles of the acid chloride was dissolved in five volumes of dry ether. The addition of the ethereal-acid- halide solution to the four moles of ethyl magnesium bromide was accomplished by means of a dropping funnel at the rate of a drop per second. The high rate of di— lution and the slow rate of addition wrs necessary to control the reaction. Also rapid and vigorous stirring (mercury sealed mechanical stirred) proved very helpful. After the last acid—halid-ether mixture was added the mixture was allowed to stir for four hours. After standing OVernight the mixture was hydrolyzed by pouring the contents of the flesh on ice and treating the resulting product with concentrated hydrochloric acid until the mixture becomes clezr. The ether-water layers were separated by the use of a separatory funnel and the remaining water solution was extracted three times with ether. The ether xtracts were combined and the ether distilled off on a water bath. The product was subjected to distillation under reduced pressure. 0 hDi—ethyl n—propyl carbinol was collected between 48 O and 48 C. at 6mm. pressure. Boiling point at 748mm. 0 0 was 155 to 155 C. The following constants were re- corded in literature as follwws: B.P. 155° to 159 c. 756mm. 0 3 o B,p, 158 to 159 c. (160.5) 760mm. ll. 0 53“: RM": I34o 0.8365 NE? 1.45216 Di-ethyl iso—propyl carbinol was collected between 54° and 560 C. at 5mm. pressure. Boiling point at 748mm. 0 0 was 156-157 The following constants were recorded in litereature as follows: B.P. 159.5 to 161 C 750mm. 3309 84655 20 eo° 11D 1.4541 1 A; o Condensations General Procedure A 500 ml. three—necked round bottom flask was provided with a mercury sealed mechanical stirrer, a tube to re- move hydrochloric acid fumes, a thermometer, and a separatory funnel. Benzene (five equivalents) was placed in a flask and the stirrer started. The entire amount of aluminum chloride (one—half equivalent) was added to the benzene and uniformly suspended in the benzene. The carbinol (one equivalent) was added by means of a dropping funnel and at a rate of a drop every five seconds. Considerable amount of hydrochloric acid was evolved during the addition of the carbinol. The temperature was maintained between 25 and 50 C. No external cooling was necessary. After all the carbinol was added the mixture was stirred an additional four hours. During the addition of the carbinol, the mixture changed from a yellow to a dark red color. The mixture was allowed to stand over night and then decomposed with ice and concentrated hydrochloric acid. The benzene layer was separated and the aqueous portion extracted several times with small portion of ether. In the ether extraction hydrochloric acid was added to destroy the ether—water emulsion. The ether and benzene extracts were washed with dilute sodium carbonate solution to remove the excess hydrochloric H 1, 1L, 0 acid and allowed to dry over calcium chloride. The ether and benzene was distilled in a fractionating column on a water bath, then the remaining mixture was subjected to reduced pressure. Di-eih11.n<2£2221 nerhinnl,_henaene and aluminum.chlnride Following the procedure above, but using one—sixth mole of the carbinol, no fractions were obtained which consisted of the desired hydrocarbon so a larger quanity of carbinol was used: Grams Equivalents (Holes carbinol 32.5 1 ' 1/4 Benzene 97.5 5 1 1/4 Aluminum chloride 8.4 1/2 1/8 The following fractions were obtained at 15mm. pressure a a l. 46 - 115 C. 7.0 grams 2. 1156— 118 C. 12.1 grams 3. above 1180 C. 3.0 grams The second fraction, after many distillations had a const— ant boiling point between 116 and 1170 C. at 15mm. and is di-ethyl n—propyl phenyl methane yield. Boiling point 0 at 745mm. 11831372237 3' x" /J 2 1""{70 The fraction between 48 — 115 C. yielded two other fractions 0 47 - 500C. @ 15mm. and 65 — 670C. @ 15mm. the former 14. consisting largely of unsaturated product (E—ethyl hexane-2) and the latter faction contained E—chloro-3~ ethyl hexane and some unsaturated compound. Equation of reaction $2H5 ) . $2H5 r‘. ' r\ ’ AlCl "T '* yr __ 0650620620 - UH + 0666K.._.g.,cnzcngc.123 - 9 _ C6H5 + 320 C2H5 CBHS Analysis of fraction Wt. of sample Wt. of Carbon-dioxide Wt.of water flc. fiH. .2160 .6966 .2249 66.20 11.65 .2070 ..691 .2155 66.15 11.64 H) Molecular wt. determination Wt. of Benzene Kt. of sample Temp. diff. H01. Wt. 17.560 .6 01 .965° 166.1 03 17.560 .5250 .776" 166.5 calculated for CléH;“")...........O.......... 190.18 65.. Di-ethyl iso-propyl carbinol, Benzene and Aluminum Chloride. The procedure, as outlined above, was followed age in, being unsuccessful in isolating any fractions containing the desired hydrocarbon when one—sixth mole of the 15. carbinol was used. Therefore the latter procedure used one—fourth mole of the carbinol; Grams Equivalents Moles Carbinol 32.5 1 1/4 Benzene 97.5 5 1 1/4 Aluminum Chloride 8.4 1/2 1/8 The following fractions were obtained at 14mm. pressure: 1. 46 - 1126 C. 8.0 grams 2. 112°- 115 c. 11.7 n 5. above 115 C. 5.0 " 0 The fraction having boiling point between 112 — 115°C. was distilled several times and a liquid having a boiling point between 1150— 1140C. at 14mm. was obtained. This liquid is di—ethyl iso-propyl phenyl methane having a boiling point between 2380— 259 C. at 745mm. pressure. 4 The yield of di-ethyl iso—propyl phenyl methane was 24.6%. The fraction between 460- 112 C. yielded two other fractions 470- 50 C.'@ 15mm. and 77:8100. @ 15mm., the former consisted largely of unsaturated product, the latter fraction contained Z-chloro—z-methyl-5_ethy1 pentane and some unsaturated product. Equation of Reaction CH5 C2H5 063 0265 \ l \ \ _. - .. I , TJL’ _______ .. _. - j n H /0 0 0L + 06.6 e H /c 0 C6H5 + Hg0 CH5 0265 0-5 C2H5 Analysis of Fraction Vt.of sample Wt.of carbon—dioxide Tt.of water .2001 .6469 .2080 .2020 .6545 .3101 a atd TT 00.0.0000...OOOOOOOOOOOO. C lcul e for C1412:23 Molecular Wt. determination 16. £0. TH. 88.16 11.65 88.11 11.64 88.30 11.69 Wt.of Benzene Wt.of sample Temp.diff. K01. Kt. 17.560 .5661 .769° 166.6 17560 .5621 .666" 166.6 Calculated for 014Hg2 .................... 190 18 l7. THLORiTICAL Theory of Condensations For condensations of alcohol, whether aliphatic or aromatic alcohols with benzene or aromatic hydorcarbons in the presence of anhydrous aluminum chloride the alpha carbon must be under strain. If we examine the electronic structure of such a system as for example allyl alcohol (I) or benzyl alcohol (II) and a tertiary alcohol (III) we can see why tertiary alcohols are able to condense. H H H H CH, "C" 0‘? 070: H Chi-1(T'C70': H CH 2070'; H '. .' .. .. o 5 -. -- Z) .. -- H H H CH5 I. II. III. The Carbon to oxygen bond is relatively unstable. This is experimentally proved by the ease with which the -OH can be replaced by a halogen from a halogen acid and also by the ease of dehydration. The electronic pair between the carbon and oxygen in I. and II. is strongly attracted by the carbon and also by the —OH group and in III. the carbon has a weak attraction but the —0H a strong attraction. The result in either case is an unstable system. Tzukervanik (32) reported the alkalation of benzene a nd toluene by use of secondary and tertiary alcohols in the presence of anhydrous aluminum chloride as a catalyst. He offered as a mechanism the formation of aluminum alcoholate which decomposed to form an alkene which in turn added hydrogen chloride to form the alkyl halide and the latter reacted with the hydrocarbon to give the alkylated hydro—carbon. This can be shown in the follow- ing steps using tertiary buyl alcohol, benzene and aluminum chloride. 1. (CH5)300H + A1015 ———-+ 21101;,300(0HE);35 + H01 2. A101200(CH5)5 -+--» 0H50=0H2 + A1C120H CH5 6. 0H30 :CH + H01 ———-> (0H5)50-01 4. (CH5)301 + 0666 --—:> (CH5)5C-C6H5 + H01 If the above codeption is correct the addition of a tertiary alcohol to a mixture of aluminum chloride suspended in an inert solvent should go throught the first three steps to the formation of the alkyl chloride. Hedrick (65) investigated the validity of the mechanism by adding normal—butyl di—methyl carbinol in petroleum ether to a suspension of Aluminum Chloride in petroleum ether. Almost instantly hydrogen chloride and heat were evolved. The mixture at first turned yellow than a I 19. deep red color. After the reaction subsided a solution of phenol in petroleum ether was added. There was no further change in color nor any evidence of reaction. After purification an 18% yield of n-butyl di—methyl p-hydroxy phenyl methane was obtained- It was noted that in the above reaction when alcohol and aluminum chloride reacted, hydrogen chloride was evolved, but by Tzukervanik’s conception no hydrogen chloride would be expected to be give off until the hydrocarbon was added. A plausible explanation for the formation of hydrogen chloride in this reaction is the dehydration of the alcohol, forming the alkene, and then the water reacting with the aluminum chloride forming hydrogen chloride and the latter reacted with the alkene to form the alkyl halide which would react with the aromatic compound to form the alkyl benzene and can be expressed by: CH5 CH5} 1 H U H ‘H*0 0* H u o c-5(Cu2)3C ' O _-d~9 bd5(CLg)5—? CH5 CH5 2. A1013 + H30 ---—9 AlClZOH + H01 922 CH7 6. CH3(CH2)3— 0 + H01 —-——e CH5(CH2)3-C ‘- 01 CFS CH3 o 0—4 0 Another mechanism is offered by McKenna and Sowa (34) who have shown that when benzene is alkylated with alcohols using boron fluoride as a catalyst the alcohol is first dehydrated and the alkene condenses with benzene according to the following scheme: H l (:3 (ca ) ca + 13F: __-_, CHQCH,.,C:C:L,' + are U 2 3 v.- p' f..- cu C. CH? ‘ t. ‘L 1" 1 u’ j' “r i H As further proof they state that normal and secondary ,alcohols give identical products and iso— and tertiary alcohols give identical products. VcGreal and Niederl (35) also supports this mechanism. A‘L More evidence in favor of such a mechanism is in the condensation of unsaturated hydrocarbons with aromatic hydrocarbons, using aluminum chloride as a catalyst. Berry and Reid (36) have shown that ethylene and benzene condense using aluminum chloride as a catalyst. Other works similar to this are numerous. Evidence against such a mechanism is slight. It must be noted that McKenna, Sowa and Niéderl used a catalyst other than aluminum chloride and a much higher temp'ra— ture than is employed in the Vnoton method. Also Huston and Sager (38) have shown that primary alcohols will not condense with benzene in the presence of aluminum chloride. In the condensation of tertiary alcohols with benzene there is no possibility of ether formation that may take place but a good yield of alkylated hydrocarbon is obtained. Huston has given as a possible mechanism the clevage of water, the hydroxyl of the alcohol and the hydrogen of the aromatic hydrocarbon combined as represented by: agcoa + H0 {Alcyfigc “06% + H20 6H5 This scheme does not account for the highly colored complex which accompanies the condensations. A plausible scheme offered for condensation of tertiary alcohols with benzene in the presence of aluminum chloride is the formation of aluminum alcoholate which adds hydrogen chloride and then splits off either hydrogen chloride or alkyl halide and then the reaction proceeds as in Tzubervanicks conception: '. 6'1: 1. R:On + Alci: _______ > h:§:Al el: + HCl fr :Cl! 3Cl'. CH O 511 O 4. Rid txrA12C1l T HCl :Cl: (:1: 1” Alzélf ;Cli . H‘,fi\lCl¢j .. K; + HCl 01‘ :61: A11le :Cl? RC1 R represents the tertiary R' represents unsaturated + C6H6 F :ci -..._._> ROf\lCl Cl .1 ~ —£Ql> ‘RcO:AlICl Cl ———-9 R' + AlClQOH —-~—9 RC1 —.Cl —5—-e RC1 + AlCleH ....._—5 RCGHS 4' HO]. alkyl group hydrocarbon Determination of Physical Constants Density measurements were made by means of a small picnometer. . 6 compared to water at 4 C. _ D All determinations were made at 20 C. Tndex of refraction measurements were made with the IC- 03 Abbe Refractometer. Surface tension measurements were made by means of the Harkins' Drop—weight Method and by the Du Nouy Tension- meter hethod. For the drop weight method, surface tension was calculat- ed from the expression: where surface tension in dynes/cm m : mass of drop in grams pull of gravity (981) n R : radius of tip (.27130 cm.) F = a constant obtained from a table corresponding to V/R° v : volume of drop (m/d) The Du Nouy Tensionmeter is a direct reading instrument. There is a correction factor necessary and that factor is given by, wt. of Cu. Wire x 981 2 x 4 x dial reading The Theoretical molecular volume was calculated by the formula, Vm : 16.27 n ~ 7.02 where n = number of carbon atoms or VIn = 16.27 n - 16.05 - 74.57 where n 2 number of carbon atoms in aliphatic side-chain 16.05 : effect of one hydrogen 74.57 — effect of phenyl ring The molecular refractions were calculated by the Lorenz— Lorentz formula, ‘ a (a N 111 1; x n — l 63 ' I Q... nb + ‘/ 6‘1 molecul ar refraction M = molecular weight d : density n index of refraction The theoretical molecular refraction was calculated from the following atomic refractions: (Zeitschrift Physical- ische Chemie,V.7, 140 L891) C — H : 1.705 C - C = 1.209 C - C = 4.151 C =7 2.148 H g 1.100 double bond g 1.733 C5 {NJ 0 The observed parachor was calculated by the formula, i=1 Fri—T X Xl/4. *‘d parachor of compound molecula weight [-70 r—‘w u d;,density X :surface tension Boilinv Points Densit' and Yolecular Volumes 6 2 0 Substance Boiling Point d-%%r 62115 257-2380 I @ 745mm. 1. n—CaH - C - C H 0 o .8788 “ 7 I 6 5 116—117 C2H5 @ 15mm. CH2 C.H 358—23 \ U 1‘ 5 @ 745mm. 2. H - C - C - CBHS o O .8816 / l 113—114 CH5 CZHS @ 14mm. Vm Theoretical Observed 1. 22 .76 216.4 2. 220.76 215.7 The molecular volumes as determined experimentally are lower than the teoretical value. The formulae used for the calculation of molecular volume only hold for straight chain compounds, therefore the theoretical value would be the value for n—octyl benzene. The difference between the theoretical and observed mole- cular volume must be due to the effect of chain branching. According to Kauffman a decrease in molecular volume is due to the heaping of eurogens on adjacent carbon atoms. Kauffmann states that the carbon atom in the benzene ring, to which is attached an aliphatic side chain, acts as a heaping center and in compounds where heaping of groups is on a carbon atom adjacent to a carbon in the benzene ring, the difference in molecular volume must be due to the groups present. Heaping of eurogens on adjacent carbon atoms decrease the mole— cular volume, therefore, the iso—compoud should possess the lower molecular volume because in the iso—compound we have a closer packing of atoms within the molecule and therefore an effective contraction in molecular volume. c: N 0 Index of Refraction and Molecular Refraction V20 in. D Substance Nfi? Calculated Observed faHs l. n—C5H7- C - C6H5 1.4968 63.25 63.30 C2H5 CH:5 CEHS \ 2. H — C — C - C6H5 1.4981 63.25 63.24 / I . CH3 CgH5 From the above data we observed and calculated values of molecular refraction agree very closely. The index of refraction of the iso-compound would be expected to be higher due to the effect of heaping eurogens on adjacent carbon atoms. Surface Tension and Parachors of the above substances surface Tension Parachors Drop-Wt. DuNouy Sugdens Calc. Harkins DuNouy 1. 30.24 82.47 519.1 516.4 506.6 516.6 2. 30.04 32.16 519.1 513.4 505.9 513.7 Sugden (39) states that for iso—merides of different structure only, parachors are identical within the I“ c- O) limits of experimental error. Also, position iso— merism seems to cause no change in the parachor". In calculating atomic structural constants, he did not consider chain—branching and therefore the parachor calculated by his atomic and structural constants are decidedly off. The values given by Sugden are: C : 4.8 Double bond : 23.2 H = 17.1 Effect of six CH2;: 39.0 membered ring : 6.1 Mumford and Phillips (40) have evaluated another series of constants in which he considered the branched chain and its lessening effect on the parachor. These con- stants are as follows: Ii-e 15.4 fouble bond := 19.0 C e 9.2 six—membered 0 a 20.0 ring = 0.8 CH23 : 40.0 The parachor, when calculated from th se constants is larger than the observed parachor. This differ— ence may be due to chain branching. Kumford and Phillips state that "chain branching in aliphatic hydro-carbons and their derivatives is accompanied by a slight but definite diminution of the parachor. The decrement varies according to the position and length of the side chain, but within the limits of experimental error a mean value of - 3.0 appears to be applicable to all branched groups of the type — CHRB and - 6.0 for — CR; radicals and double branch- ed compounds of the type CHE .........CHRQ IQ A; When these decrements are used the calculated parachor checks more closely with the observed parachor. A closer check is obtained if a decrement of - 3.0 is used for branching on a phenyl ring. The calculated value of parachor in the above table includes this decrement. It is shown in this table that the cal- culated parachor now checks very clsoely with the observed parachor calculated from surface—tension values determined by the ruNouy method. 1 surface-tension values determined by the drop weight method are lower than those determined by the DuNouy method. Therefore, the Drop-Weight parachors are lower than the EuNouy parachors. This seems to suggest that a new set of constants must be introduced for the DrOp—Weight method for this series of compounds. SUifi-Ivflihy l. Tertiary octyl aliphatic carbinols condense with benzene in the presence of aluminum chloride, according to the equation: R R l | a' - C - OH 4 CBHG {Alglsls at — c - c6925 + HQO ) ‘ b R R WherrR' is n—propyl or iso—propyl group and R represents the ethyl group. 2. Physical constants, as boiling points, index of refraction, molecular refractions, molecular volumes, surface tension, and parachors were determined for each compound. 3. The relationship between structure andphysical properties is shown. BITLIOURAPHY (1) Becher Ber. 15, 2090 Noelting " 24, 5126 Gattermann and Koppert " 28, 2810 Bistrzycki, Flatau 'and Simonis " 38, 989 Meyer " 6, 984 El, 5812 Fritsch and Theil " 29, £300 (2) Fischer and Roser " 13, 674 Liebmann " 14, 1842 Merz and Weith " 14, 187 Auer " 17, 669 Kippenbers " so, 1141 (E) Hemilian " 16, 2560 Michael and Jeanpretre " h5, 1615 (4) Khotinske & Patzewitch " 24, 3104 Szeki Acta. R 2,5 (5) Neyer & hurtzer Ber. 6, 965 Pateno & Filiti Gaza. chim. ital. 5, 381 Bistrzycki & Gyr Ber. 57, 655 Mohlau & Klopfer " an, 2147 (6) Eazzara Gaza. chim. ital. 12, 505 _ “or (‘rl (7) (8) (9) (19) (ll) <12) <12) (l4) (15) ((16) Michael & Jeanpretre Bistrzycki Noelting Friedel and Craft Herz & Weith Frankforter Prins Dougherty Vohl & tertyporoch Huston & Friedemann Huston & Friedemann Huston Ff) Co 0'3. CD *3 & Huston & ; '0 Q) 0‘; CD *3 Huston &Goodemoot a Hradel 1.. 1 C U) (.1. O {:5 Huston & Macomber Rer. 25, 1615 " 5 , 659 " L4, 553 Comp. Bend. 84, Ber. 14, 187 " l5, lla8 " E4, 1778 J. Amer. Chem. 56, 1511 57, 585 Chem. Weekblad J. Amer. 51, 576 Ber. 64, 1357 J. Amer. Chem. 58, 2537 J. Amer. Chem. 40, 785 Unplublished J. Amer. Chem. 48, 1955 J. Amer. Chem. 56, 2452 C») 1 C )1 C D 800. 24, 615 Chem Soc. Soc. (1916) Soc. (1918) 900. (1926) Soc. (1934 Hradel's Master Thesis Macomber's Raster Thesis (17) (18> (19> (20) (21> (24> (25> (26> (27> (2.8) (29) (20> (31> O] (‘N Huston & Hsieh J. Amer. Chem. Soc. 58, 439 (1936 Huston & fox Fox's Master Thesis Huston and Binder Binder's Master Thesis Huston a Sculati Sculati's Faster Thesis Fittig Ber. 8, l7 Baeyer Ann. 140, 295 (1866) Libmann Ber. 15, 45 (1880) Gearhardt & Cahours Ann. 38, 88 (1841 Fettig Ann. 131, 305 (1861) Friedel & Craft Compt. Bend. 84, 1392 (1877) Gilman—Organic Synthesis Coll. Vol. I, 458 (1933) Klage Ber. 55, 2655 (1908) 57, 1447 (1904) Bercker Ann. Chim. Phys. (5) 26, 468 (188z) J. Amer. Chem Soc. 5, 1561 (1933) 45, 150, 159 2462 (1923) 51, 1576 (1929) Tren The Organo-Metallic Compounds of Zinc and magnesium Zeitschrift fur physicalische chemie 29, 258 Belstein's Organisbhen Chemie Band I 121, 156, 162, 164, see Clarke Riegell J. Amer. Chem. 800. 34, 54, 677 (1912) Clarke Riegell Halse $2) Tzukervanik (ES) Huston & Hedrick (54) McKenna & Sowa (35) McGreal 4 Niederl (36) Berry & Reid (57) Varet Cline & Reid Copenhaver & Reid Bodroux (68) Huston & Sager (59) Sugden (40) Mumford & Phillips QZChem.Soc. Abstracts 64, 124 (1895) J.Pr. (2) 89, 454 J. Gen. Chem. (U.S.S.R.) 5, 117, 764-67 (1955) C.A. 29, 4746 (1929) 0.4. 30, 445 (1926) Hedrick's Doctor Thesis (1927) J. Amer. Chem. Soc. 59, 470 (1936) J.fimer.Chem.Soc. 57, 2625 (1955) J.fimer.Chem.Soc. 49, 5142 (1927) Compt. Bend. 164, 1675 (1886) J.Amer.Chem.Soc. 45, 5150 (1927) J.Amer.Chem.Soc. 49, 5157 (1927) Compt. rend. 186, 1005 (1928) J.fimer.Chem.Poc. 48, 1955 (1926) J.Chem. 900. 125, 1177 (1924) J.Chem. Soc. (London) 55, 2112 (1929) .I... 1 .1 {#4) . .'-T.Ilplu»°'§ 14.! «I ”1.1"... I. 11" 5., Gillian ‘iw 10w}! I‘lfiwulw Il‘ . 0 ! .1..J I‘lr 1.4!«4 I" Q‘s