Oct., 1937
ALUMTNUM CHLOR~DE CONDENSATION OF ~-HEFTANOLS WITH PHENOL [CONTRIBUTION FROM THE
2001
KEDZIECHEMICAL LABORATORY, MICHIGAN STATE COLLEGE]
Condensation of the Tertiary Heptyl Alcohols with Phenol in the Presence of Aluminum Chloride BY R. C. HUSTON AND G. W. HEDRICK' A previous paper from this Laboratory2 de- structure of the phenols for as the heaping inscribed the condensation of t-butyl, t-amyl, and creases there is a decided increase in the melting the three t-hexyl alcohols with phenol in the pres- point. ence of anhydrous aluminum chloride. To study All of the t-heptyl alcohols are found in the further the scope of the reaction the following literature. 3-' tertiary heptyl alcohols, wz., n-b~tyldimethyl,~. Good yields were obtained in every case with i~obutyldimethyl,~ s - b~tyldimethyl,~ t - butyldi- the exception of isopropyfmethylethyl- and tmethy1,4p6n-propylmethylethyl, isopropylmethyl- butyldimethylcarbinols. For these new syntheethy1,B and triethyl' carbinols were prepared and ses were employed. The first was made by concondensed with phenol. A yield of from 25 to densing methyl isopropyl ketone and ethylmag65% of a p-t-alkyl-phenol was obtained and no nesium bromide; and the latter by condensing other isomers could be isolated. The benzoyl pinacolone with methylmagnesium iodide. and o-chlorobenzoyl esters, and the cu-naphthylExperimental urethans were prepared. Isopropylmethylethylcarbino1.-Thirty-six grams ( 1.5 The structure of the alkylphenols was estab- moles) of magnesium and 200 cc. of anhydrous ether were lished by synthesis. In an unpublished paper8 placed in a one liter three-necked flask equipped with a Huston and Binder condensed all the t-heptyl mercury-sealed stirrer, a reflux condenser and a dropping alcohols with benzene and identified the alkyl- funnel. To this 153.5 g. (1.5 moles) of dry, redistilled ethyl benzenes by molecular refraction, parachor, den- bromide was added with stirring through the dropping a rate fast enough to keep the mixture refluxing sity and molecular volume determinations. These funnel a tAfter the addition was complete, the stirring was gently. alkylbenzenes were nitrated, reduced, diazotized continued for one hour at room temperature. Then 130 and hydrolyzed to the phenols. The melting g. (1.5 moles) of isopropyl methyl ketonela in 200 cc. of points and mixed melting point determinations anhydrous ether was added dropwise. After the ketone was all added stirring was continued of the a-naphthylurethans of the phenols thus prepared indicated that they were the same as a t room temperature for two hours, then the mixture was decomposed. The usual methods for decomposition were those prepared in the condensation^.^ The po- employed. Eighty-seven grams of the alcohol, boiling at sitiori was established by oxidatioii 6f thc p- 50-52" (20 mm.), 1.4283was obtained which was 50% iiitro-t-alkylbenzene by the Carius method to of the theoretical yield based on the ketone. t-Butyldimethylcarbinol.-The same procedure and the p-nitrobenzoic acid which was identified by its same proportional quantities as in the above were emmelting point and mixed melting point.2 ployed. Thus 128 g. (0.9 mole) of pinacolone yielded More evidence in support of the structure is 75 g. of the alcohol which boiled a t 48-51' (20 mm.) boriie out in the physical properties. By ob- (71% of the theoretical yield). This consisted of a mixserving the properties listed in Tables I, 11, 111, ture of colorless crystals (m. p. SOo) and a liquid which and IV, it is obvious that the seven phenols are solidified when cooled in ice. This corresponds to the carbinol described by W h i t m ~ r e . ~The alcohol was used all different. It is known also that the heaping without further purification for the condensation with of eurogens on adjacent carbon atoms of a com- phenol. pound causes an increase in the melting point Condensations.-Inasmuch as all the condensations of the compound. This fact is in support of the were carried out in a similar manner only a typical run is (1) From a thesis submitted in partial fulfilment of the requarements for the degree of Doctor of Philosophy (2) R C. Huston and T Y Hsieh, THIS JOURNAL, 58, 439 (1936) (3) Whitmore and Church, { b i d , 65, 1119 (1933). (4) Edgar, r b t d , 61, 1483 (1929) ( 5 ) Whitmore and Badertscher, r b i d , 66, 1559 (1933). (6) Whitmore and Evers. $ b i d , 66, 812 (1933). (7) "Orgaluc Syntheses," 13, u) (1933). ( 8 ) Huston and Binder, Masters Thesis, Michigan State College, 1933. (9) N o urethan of the l-butyl derivative was prepared. The phenol itself was identified.
described here. Twenty-nine grams (0.25 mole) of nbutyldimethylcarbinol and 28 g. (0.30 mole) of phenol dissolved in 100 cc. of petroleum ether was added dropwise with stirring over a period of two hours to 17 g. of anhydrous aluminum chloride (0.125 mole) suspended in 150 cc. of petroleum ether. The addition was carried out a t room temperature (2O-3O0)l1 during a period of four to (10) "Organic Syntheses," 13, 68 (1933). (11) Isopropylmethplethylcarbinoland s- and f-butyldimethylcarbinols were added to the suspension kept at 0-10'.
2002
R. C . HUSTON AND G. W. HEDRICK
VOl. 59
TABLE I
CONDENSATION OF I-HEPTYL ALconoLs WITH PHENOL Product, p-hydroxy phenylmethanes
-
Yield,
%
n-Propylmethylethyl-lz n-ButyldimethylIsobu tyldimethylIsopropylmethylethyls-ButyldimethylTriethyl&Butyldimethyl-
30.7 64.6 44.4 40.6 27.3 30.0 25.8
‘C.
.....
124.6 123.5 115-117 125-127 117-119 120-122
16-17 31-32 42-43 49-50.5 75.5-76.5 133-134
six hours. The mixture was allowed to stand overnight, then decomposed with ice and hydrochloric acid. The phenol was isolated by fractionation. Table I includes a summary of the results. For further purification the phenols were pressed between filter paper and then recrystallized using 50% alcohol-petroleum ether solution. The benzoyl and o-chlorobenzoylesters were prepared by the method described by Shriner and Fuson.13 After isolation the esters were distilled under reduced pressure, recrystallized first from an 85% alcohol solution and then an 85-90% acetic acid-water solution. The results are collected in Tables I1 and 111.
TABLE I1 BENZOYL ESTERS OF +~-HEPTYLPHENOLS Compound p-hydroxyphenylmethanes
M. p., OC.
n-Propylmethylethyln-ButyldimethylIsobu tyldimethylIsopropylmethylethyls-ButyldimethylTriethylt-Butyldimethyl-
38-39 36-37 71-72 4041 44-45 74-75 84-84.5
Analyses of CisH?dO? Carbon, % Hydrogen, % Calcd. 81.03 Calcd. 8.16
80.40 80.91 80.42 80.61 80.39 81.09 81.01
8.16 8.10 8.12 8.28 8.00 8.19 8.15
The a-naphthylurethans were prepared by the method of Shriner and Fuson13 (p. 63). The urethan of the tbutyl derivative could not be purified due to its extreme insolubility. The results arc listed in Table IV.
TABLE I11 0-CHLOROBENZOYL ESTERSOF P-t-HEPTYLPHENOLS Compound $-hydroxyphenylmethanes
n-Propylmethylethyln-ButyldimethylIsobutyldimethylIsopropylmethylethyls-ButyldimethylTriethyl&Butyldimethyl-
B. p. (2 mm.) M. p., ‘C.
25-26
OC.
...
.,
177-179
51-52 4243
... ...
...
175-178
,
67-68 83-85
... ...
Boiling points Mm. C.
M. p., OC.
Analyses of Ci8HzdhCI Chlorine, % Calcd. 10.73
10.68 10.71 10.63 10.59 10.64 10.81 10.62
Proof of Structure of the t-Heptylpheno1s.-The nicthod ciiiployed was the sanie as that used by Huston and Hsieh2 (12) McCredl and h’ietlerl, THISJOURPI’AL, 57, 2623 (1036). (13) Shriner and Fuson, “The Systematic Identification of Organic Compounds,” Edwards Brothers, Ann Arbor, Mich., 1933, p. 62.
‘
4 4
4 4 4 4
278.5 277 273 272 281 275 287
Anal of CisHz00 Carbon, % Hydrogen, % Calcd. 81.18 Calcd. 10.49
Mm.
748.5 749.5 748.5 748.5 748.5 749.5 748.5
80.75 80.58 80.88 80.66 80.81 81.11 80.82
10,49 10.39 10.47 10.24 10.44 10.49 10.34
TABLEI V a-NAPHTHYLURETHANS O F P-t-HEPTYLPHENOLS yo N in
9-Hydroxyphenylmcthanes
n-Propylmethylethyln-ButyldimethvlIsobutyldimethylIsopropylmethylethyls-ButyldimethylTriethylt-Butyldimethyl-
CiiH?702N? Calcd. 3.87
M. p . , O C .
82.3 110-1 1 114-115 112-113 122-23 133-35
3 84 3.87 3.78 3.92 3.79 3.91 ..
...
with two exceptions. I n nitrating the alkylbenzenes, after the ihitial reaction had subsided, the acid mixture was warmed to 90” for two hours on the steam-bath, and the procedure for reducing was the same except that eight to ten hours was employed instead of two hours. The p-theptylphenylamines and nitro compounds and their properties are listed in Tables V and VI.
TABLE V +NITROt-HEPTYLPHENOLS p-Nitrophenylmethanes
n-hopylmethylethyln-ButyldimethylIsobu tyldimethylIsopropylmethylethyls-ButyldimethylTriethylt-Butyldimethyl- (solid)
M. or b. p., OC. (741 ram.)
% Nitrogen in CisHisOsN Calcd. 6.39
B B B B B B
292 291 284 285 277 282 M 108
6.31 6.31 6.25 6 24 6.29 6.30 6 33
TABLE VI #-AMINO-~-HEPTYLPHENOLS % Nitrogen p-Arhinophenylmethanes
n-Propylmethylethyln-ButyldimethylIsobutyldimethylIsopropylmethylethyls-ButyldimethylTriethylt-Butyldimethyl- (solid)
M. p. o r b . p ‘C, mm.
B B B B B B M
117-8 145-6 124-5 146-8 120-1 128-31 55-56
5
10 5 11 5 5
..
in CisHziN Calcd. 7.17
6.98 7.22 7.06 7.01 6.87 7.21 6.90
Summary 1, The aliphatic tertiary heptyl alcohols condense with phellol in the preserlce of alumilium chloride to give p-t-heptylphenols.
Oct., 1937
QUANTITATIVE
2. The benzoyl and o-chlorobenzoyl esters and the a-naphthylurethans of the seven phenols were prepared.
[CONTRIBUTION FROM
THE
2003
ACETYLATION OF AMINES
3. The structure of each of the seven phenols was established by synthesis. EASTLANSING,MICH.
RECEIVED JULY 26, 1937
DEPARTMENT OF CHEMISTRY, WORCESTER POLYTECHNIC INSTITUTE]
Quantitative Acetylation of Amines by Means of Acetyl Chloride and Pyridine BY VERNER R. O L S O N AND ~ , ~ HARRYB. FELDMAN s
In the case of organic hydroxy compounds, of the acetylation from 60 to 70” led to materiSmith and Bryant3 recently have developed a ally increased yields for many of the compounds rapid and precise method for the quantitative investigated. Only those compounds which were determination of primary and secondary hy- found to be very unreactive using the original droxyl groups. Their method consists essen- Smith-Bryant method or were particularly sentially in modifying the usual acetic anhydride- sitive to the action of light and heat yielded acetyl pyridine acetylation mixture by the substitution values less than 90% of the theoretical. The results secured using acetyl chloride and of acetyl chloride for the anhydride, the acetyl chloride being a more reactive acetylating agent. pyridine dissolved in di-n-butyl ether as an acetyThe above mentioned authors found that pri- lating medium indicate that in addition to servmary and secondary amines as well as mercaptans ing as a quantitative method for estimating cerreacted with the acetylating medium to an ex- tain amines and amine derivatives, this procedure tent not determined by them and they suggested may serve as a convenient simple method for that these types of compounds might be esti- preparing small amounts of the diacetyl derivatives. mated by their method. In the present work the applicability of the Experimental Smith-Bryant reagent as a quantitative acetylatReagents.-The original acetylating mixture was the ing agent was tested on a wide variety of amines same as that used by Smith and Bryant. Acetyl chloride as well as on a limited number of amine deriva- (E. K. C. Practical) was dissolved in Mallinckrodt “Anatives such as hydroxyamines, amine hydrochlo- lytical Reagent” toluene which previously had been dried rides, amides, anilides, etc., and on thiophenol. over sodium. In the modified reagent, the toluene was I t was found that for some compounds practically substituted by di-n-butyl ether (Commercial Solvents Corporation) which had been rendered peroxide free by quantitative results could be obtained, while in the method of Brandt.* The boiling point of this reagent the case of other compounds various factors such was 141”. Pyridine used in conjunction with the above reas insolubility in the acetylating medium, low rate agents was made anhydrous by the method of Zerewitinoff , 5 Compounds Acetylated.-A few of the compounds of reactivity due to the presence of certain substituents, decompositionof the amine during acety- investigated were obtained from the Eastman Kodak Co., the Mallinckrodt Chemical Co. The greater portion lation etc., materially decreased the yield of and were prepared by the authors and were repeatedly recrysthe acetylated compound and indicated the gen- tallized or distilled until they were a t least 99% pure. eral inapplicability of the Smith-Bryant method. All materials employed were desiccated for at least twentyAn increase in the relative amount of pyridine four hours before use. Analytical Procedure and Apparatus.-The analytical in the acetylating reagent resulted in immaterial procedure and apparatus, except for the modifications changes in the determined acetyl values. described below, were the same as those used by Smith Variation of the acetylating reagent solvent and Bryant.a disclosed the fact that substituting di-n-butyl In place of the 250-cc. g. s. volumetric flasks, 300-cc. ether for toluene and increasing the temperature long-necked, round-bottomed Pyrex flasks were used. ( 1 ) Abstracted from a thesis by Verner R. Olson. submitted to the Faculty of Worcester Polytechnic Institute in partial fulfilment of the requirements for the Degree of Master of Science. June, 1937. (2) Present address: E . I . du Pont de Nemours & Co. Inc., Finishies Division. Philadelphia, Penna. (3) D. M. Smith and W. M. D. Bryant, THIS JOURNAL, 67, 61 (1935).
As a means of dispensing the acetylating reagent, a 10cc. calibrated pipet was used. A rubber syringe bulb was attached to the end of this pipet by means of a rubber tube bearing a spring pinchcock. (4) Brandt, Chem.-Zfg., 61. 981 (1927). ( 5 ) Zerewitinoff, Z. a n d . Chcm.. 60, 683 (1911)
