TAe J o u r n a l o£
P ublished "Monthly by The American Chemical S ociety
Advisory Board: H. E. Ba r n a r d Ch a s. L. Re e s e Ed i t o r i a l Op f i c b s:
One M adison A venue, R oom 343 N ew Y o rk C ity Te le ph o n e: G ram ercy 0613-0614
Editor: CHAS. H . H E R T Y A ssistant Editor: L o is W . Wo o d f o r d
J. W. Be c k m a n A. D. Li t t l e A. V. H. Mo r y Ge o. D. Ro s e n g a r t e n
C able A ddress: J IE C H E M
T . B , Wa g n e r
Ad v e r t is in g De p a r t m e n t: 170 M etro p o lita n T ow er
N ew Y o rk C ity Te l e p h o n e: G ram ercy 2145
Volume 13 J U N E 1. 1921
No. 6
CONTENTS Editorials:
Welcome to Madame Curie... 502
A T ragedy A verted... 502
A Call to Service... 503
Less Legislation—More Cooperation... 503
Original Papers: The Alkylation of Aromatic Amines by Heating with Aliphatic Alcohols. Arthur J. Hill and John J. D onleavy ... 504
Precipitation of Grain-Curd Casein from Pasteurized Milk, Including Sweet Cream Buttermilk. Harper F.Z oller... 510
The Relations of Hydrogen-Ion Concentration to the H eat Coagulation of Proteins in Swiss Cheese Whey. Yuzuru Okuda and Harper F. Zoller... 515
The Variability of Crude Rubber. John B. T uttle 519 The Relation of Moisture Content to the Deterioration of Raw-Dried Vegetables upon Common Storage. H. C. Gore and C. E. M angels... 523
Manganese in Commonly Grown Legumes. J. S. Jones and D .E .B u llis ... 524
Effect of Heat on Different Dehydrated Vegetables. C. E. Mangels and H. C. Gore... 525
Methods for Determining the Amount of Colloidal Material in Soils. Charles J. Moore, William H. Fry and Howard E . M iddleton... 527
A Dry Method of Preparing Lead Arsenate. O. W. Brown, C. R. Voris and C. O. H enke... . 531
The Determination of Dicyanodiamide and of Urea in Fertilizers. Erling Johnson... 533
Yield and Composition of Wormwood Oil from Plants at Various Stages of Growth during Successive Seasons. Frank R abak... 536
Studies in Synthetic Drug Analysis. V III—Estima tion of Salicylates and Phenol. W. O. Em ery 538 The Determination of Cobalt and Nickel in Cobalt Steels. G. E. F. Lundell and J. I. Hoffman... 540
Improved Denigès Test for the Detection and Deter mination of Methanol in the Presence of Ethyl Alcohol. Robert M. Chapin... 543
Determination of Refractive Indices of Oils. Henry S. S im m s... 546
Microanalytical Methods in Oil Analysis. Augustus H. Gill and Henry S. Sim m s... 547
The Determination of Small Amounts of Lead in Brass. Francis W. Glaze... 553
Laboratoryand Plant: The Manufacture of Citric Acid from Lemons. C. P. Wilson... 554
Apparatus for the Rapid Determination of the Avail able Chlorine in Bleach Liquor. Morris Schrero.. . . 559
N o te s on Laboratory Apparatus. A. B . Andrew s...
E lectric Muffle Furnaces for Laboratory U se. H . C.
K rem ers...
A N ew T y p e of E lectrolytic Cell. Hiram S. L u k en s. . . W ater H eater for A n alytical W ork. S. L. M ey ers...
Addresses and Contributed Artic les:
A lcohol and the Chemical Industries. J. M . D oran___
Social Industrial Rela tio ns:
Crowds and Their M anners. H . W . Jordan...
Scientific Soc ie t ie s:
N ich ols M ed al Awarded to G ilbert N . Lewis; Chemical Societies Honor M adam e Curie; A. C. S. Com m ittee R eports; D ivision of Industrial and Engineering C hem istry— Su bm ittal of Papers; H o tel A ccom m o
dations, American Chem ical S ociety M eetin g, N ew Y ork C ity, Septem ber 6 to 10, 1921; D ivision of C hem istry and Chem ical T ech nology of th e N ational Research Council; T he E xposition of Chem ical In dustries; T he N a tion al Lim e A ssociation; Calen
dar of M eetin g s...
Notesand Corr espon den c e:
M adam e Curie R eceives Gram of R adium and M any Honors; Presentation of M edal to Dr. Frederick B.
Power; T he D irect Id en tification o f S oy-B ean O il;
N e w Chemical Laboratories; E xchange Professors in Engineering and A pplied Science betw een French and American U n iversities; T h e D etection of Phenols in W ater—C orrection...
Misc ella n eou s:
Annual T ables of C on stan ts...
Dr. Chandler R eceives N a tion al In stitu te of Social Sciences M ed a l...
T he N ational Fertilizer A ssociation ...
T he Belgian B ureau of Chem ical Stan d ard s...
C entennial of Philadelphia College of P harm acy...
Cryogenic Laboratory, Bureau of M in e s...
Bureau of E m ploym ent of the N ew Y ork C hem ists’
C lu b ...
Am erican In stitu te of Chemical E ngin eers...
Washington Le t t e r...
London Le t t e r...
Pa ris Le t t e r...
Industrial N o t e s...
Personal No t e s...
Governm ent Pu b l ic a t io ns...
Book Re v ie w s...
New' Pu blicatio ns...
Market Re po r t...
560 561 562 563 564 566
567
573 509 530 535 539 539560 563 563 575 576 576 577 578 580 583 586 587
Subscription to n on-m em bers, $7.50; single copy, 75 cen ts, to m em bers, 60 cen ts. F o reig n p o stag e, 75 c en ts, C an a d a , C u b a an d M exico excepted.
S u b scrip tio n s a n d claim s for lost copies should be referred to C harles L . P arso n s, S e c re ta ry , 1709 G S tre e t, N . W , W ash in g to n , D. C.
502 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 13, No. 6
EDITORIALS
Welcome To M adam e Curie!
W elcome, thrice welcome, to our distinguished h o n orary m em ber, M adam e Curie!
Since the day of her arriv al she has been over
whelmed w ith honors and w ith en te rta in m e n t, alm ost to th e d etrim en t of her physical h ealth . She has in spected th e p lan ts where rad iu m and o th er rare m ineral salts are produced, and carries hom e increased facilities for continuing her research. She has come into touch w ith our bustling A m erican life, and perhaps when she gets back to th e quiet of her la b o ra to ry she will tell us w h at she th in k s of it all. H er presence has em phasized w ith o u t th e necessity of words th e g reat value of fu n d am en tal chemical research and th e possi
bilities for tho ro u g h ly equipped wom en in chem istry.
H er visit has proved a fitting and delightful m eans of em phasizing again th e stre n g th of th e tie th a t binds France and America.
A T ragedy Averted
A new ch ap ter in th e fight for th e pro tectio n of th e Am erican coal-tar chem ical in d u stry opened on April 26, 1921, when S enator K nox intro d u ced in th e Senate Finance C om m ittee an am endm ent to th e E m ergency Tariff Bill continuing for six m onths th e regulations controlling th e im p o rtatio n of coal-tar chemicals, which were in danger of im m ediate abro g atio n should th e K nox peace resolution become law . T his law would au to m atically te rm in a te th e T rading-w ith-the- E nem y A ct, under which th e W ar T rad e B oard Section of th e S ta te D ep artm en t had been functioning. Senator Knox was sim ply acting in good faith , to preserve for th e sole in d u stry affected by his peace resolution th e protection which he recognized was necessary for its very existence. T he am endm ent m ade no change ex
cep t to tran sfer th e a d m in istrativ e m achinery from the S tate D e p a rtm e n t to th e T reasu ry D ep artm en t.
T he Finance C om m ittee accepted the am en d m en t and th e bill was rep o rted favorably to th e Senate. T hen w hat a howl was raised! Senator Moses was n a tu ra lly th e high soprano in th e very lim ited b u t noisy chorus of opposition. Senator K nox disposed of th e Moses objections p ro m p tly an d effectually w hen he refused to view the m atte r from the “ sta n d p o in t of a profit and loss account of a D olly V arden calico mill in New E n g lan d .”
T he word “ m onopoly,” used by S enator M oses in referring to th e A m erican dye in d u stry , fell like honey—
no, ra th e r som ething highly stimulative^—in to th e w ait
ing m ouths of Senators K ing and H itchcock. T he result was a flood of oratory. All of th e fam iliar stock phrases which characterized th e “ tru st-b u ste rs” of old were resurrected.
B oth Senators were deeply im pressed by th e large exports of A m erican dyes during th e p a st few years, no t caring to tro u b le them selves a b o u t looking in to th e character and conditions of this export business.
T hey could have learned th a t it represented th e n a tu ra l A m erican genius for mass production where m ethods
have been thoroughly stan d ard ized , and th a t th e prod
ucts were m arketed a t a tim e w hen th ere were no other available sources of dyes. T hey could easily have learned of th e trem endous drop in dye exports during th e p a st six m onths, as show n in th e following table from figures issued by th e D e p a rtm e n t of Commerce.
Ex p o r t s o p An i l i n e Dyf.s
N o v em b er 1920 $2,006,534
D ecem ber 1920 1,788,170
J a n u a ry 1921 943,595
F e b ru a ry 1921 397,123
M arch 1921 574,969
April 1921 305,760
A few days la te r S enator K ing exclaim ed “ th is vora
cious tr u s t is determ ined to p e rp e tu a te in peace times w ar policies an d fasten upon th e people an obnoxious and vicious system u nder which it m ay conceal its acts of spoliation an d ro b b e ry .” B u t w h at evidence is th ere of a tru st? N o interlocking directo rates were m entioned, no op eratin g agreem ents were exposed, no uniform fixed prices were quoted by th e Senator, nor was any ten d en cy of large concerns to swallow up small ones reported.
T here is no A m erican dye tru s t, an d th e fa c t is well known. T he sm all m an u factu rers are on record be
fore th e Senate ( Congressional Record, Ju n e 3, 1920, pages 8306-8) in a p etitio n urging favorable protective legislation, w ith o u t w hich th e y m a in ta in th a t they will be th e first to go down in th e struggle w ith th e real dye tr u s t in G erm any.
T here is no tendency to hold up th e A m erican people w ith e x o rb itan t prices, as shown by th e following schedule of prices of ty p ical articles, obtain ed on the s tre e t a few days ago:
Dy e s Pr ic e a Ye a r Ago Pr ic e To-day
O range I I ... $ 0 .8 5 $ 0 .5 0 D irect B la ck ... 1 .2 0 0 .7 5 G allo cy an in e... 4 .2 5 2 .5 0 Fuchsin C ry s ta ls ... 5 .5 0 2 .7 5 M alach ite G reen C ry s ta ls ... 4 .5 0 2 .0 0 M eth y len e B lue T e c h n ic al... 3 .7 5 2 .4 0 In t e r m e d ia t e s Us e df o r Dy e s
Aniline O il... 0 .3 7 0 .1 8 B e ta -N a p h th o l... 0 .8 8 0 .3 2 P a ra -N itro a n ilin e ... 1.7 5 0 .8 0 Ot h e r In t e r m e d ia t e s
G am m a A cid ... 6 .0 0 3 .2 5 B enzidine, B ase... 1 .5 0 1.00 D im e th y la n ilin e... 2 .2 0 0 .4 2 P a ra -P h cn y le n e d ia m in e ... 2 .5 0 1 .75
I t was S enator K ing who, in th e last Congress, rushed in a bill to resto re alien p ro p erty a n d holdings seized during th e war. T his m ay be a mere coincidence, of course. T he bill was n o t rep o rted o u t of com m ittee, b u t th e Senator, n o th in g d au n ted , rein tro d u ced the th e bill soon afte r th e p resen t Congress convened.
A t th e conclusion of S enator H itchcock’s address, Senator K nox com m ented ( Congressional Record, M ay 11, 1921, page 1285):
I only wanted to observe that there is something entirely familiar in these lamentations of the Senator from Nebraska about the probability of the German monopoly in the most dan
gerous munitions that have ever been manufactured being inter
fered with by this bill. We remember that during the war, when the Germans had a monopoly of munitions and the Allies could not obtain munitions to fight the Huns the Senator from Nebraska advocated a bill to prevent the people of the United States from
June, 1921 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 503 shipping munitions to the French and to the English and to the
Italians, who were engaged in a death struggle with Germany for the preservation of civilization.
W hen th e tim e cam e for voting, th e am en d m en t was overwhelm ingly a d o p ted by th e Senate. I n conference the d u ratio n of th e pro tectio n afforded by th is “ Dye and Chem ical C ontrol A ct, of 1921,” was lim ited to three m onths. T he bill continues th e licensing of im portations as h ith e rto carried o u t, except th a t th e power is vested in th e C ustom s Division of th e T reasu ry D epartm ent, w here it logically belongs.
The a c t was signed by P resid en t H ard in g on M ay 27, 1921. A near tra g e d y has been av erted , b u t th e end is n o t yet.
A Call to Service
Our organic chem ical in d u stry has been spared a m or
tal blow. T he flood gates h av e n o t been opened for the in ru sh of th e accu m u lated G erm an stocks of dyes and o ther sy n th etic organic chemicals.
B ut th e fight is n o t y e t over. Those who desire opportunity for u n restricted im p o rta tio n are working bitterly. W itness th e following le tte r sen t to a con
sumer of dyes by a firm of im p o rters whose record shows all too clearly th eir T eutonic connections:
KUTTROFF, PICKHARDT & CO., Inc.
D Y E S T U F F S . C O L O R S A N D C H E M I C A L S
. l'jiy 25 . 1921
JOS WEST RANDOLPH IT
G e n t le r a n : -
a re n d r js e d t h a t t h e C o a n itte e on Vny* «nd Venn*
l e > roponlr.g t o In clw -e tr.e Sye L ic e n s e P ro v im o n In th e P « r- c a r.e n t T a r i f f ,
In y o u r p r n ln tn r< i* t i t 1b o o e t In o n rtn iit t h * t you
»end lTTsedltitoly io your r e p r o r e n tu tlv # on th e f o - w itte e . th e Con. J c e . A. F ro n r, v ig o ro u s te le g rn n , o f _r>rotept n g a in e t a ry L ic en c e o r S p a r g e r e * t r i c t i n g th e i n p o r t n tl o n o f d .'e * tu f f * .
; < l t t e r L ic e n se o r Ksbargo .-scan* n o n o p o ly , »hare*« a e t r a l g h t t a r i f f would e A f e g n rd fcwth dve j t o f f n a n u f a c t u r r r e and c o n - euraere.
Yours r o e p e c t f u l l y ,
U,IID
HAOCOUT-
A c* . MAY 2 6 m AWS._
e* tx _
W hat is th e best m ethod of overcom ing th is oppo
sition an d insuring p erm an en t legislation which will preserve to th is n a tio n th e invaluable asset of a com plete coal-tar chem ical in d u stry ? I t is only neces
sary to tell th e whole stra ig h tfo rw a rd sto ry in lan guage w hich th e m an on th e stre e t can u n d e rsta n d . Show th e organic chem ical in d u stry as it existed (or didn’t exist) before th e war, conditions during th e war, and happenings (legislative an d otherw ise) since th a t time. T he sto ry of chem istry alw ays effects a d y nam ic conviction which expresses itself in definite
action. C ontinued education is needed as to its signifi
cance for econom ic independence and n ational defense.
T he daily press is doing splendid work, b o th in its editorial and news colum ns. T he Chem ical F o u n d a tio n is playing an im p o rta n t p a rt th ro u g h its d istrib u tio n of D r. Slosson’s book “ C reative C h em istry .”
65,000 copies of this fascinating, illu m in ativ e sto ry of chem istry have alread y been d istrib u ted to leaders of th o u g h t in every sta te . T he Com m issioner of E d u c a tion has d istrib u ted th e p am p h let “ T reasure H u n tin g of T o -d ay ” to every high school in th e land. U nder th e auspices of th e N atio n al R esearch Council th ere has been p repared by th e Chem ical W arfare Service an exhibit, including a topo g rap h ic model in relief, ch arts, and specim ens, showing th e close relatio n s of th e various lines of chem ical in d u stry . T his exhibit was show n n o t long ago in th e C apitol in W ashington, where it was closely studied by m em bers of Congress, an d has now been p erm an en tly established in th e N atio n al M useum .
In th is w ork of fu rth erin g public u n d erstan d in g you, fellow chem ist, have your responsibility. Are your neighbors, your business associates, your com m unity thinkers, fam iliar w ith th e facts? T alk to a group—
speak before your R o ta ry Club— address th e local C ham ber of Com m erce. A rrange for an exhibit som e
where in your city. T his is n o t th e business of any sm all group of m en, b u t a ta sk for each individual chem ist to share.
Less Legislation—M ore Cooperation
To m eet th e g reat difficulties being experienced in enforcing th e prohibition featu re of th e N atio n al P ro hib itio n A ct a new enforcem ent bill has been intro d u ced in to Congress. P o p u larly it is know n as an anti-beer bill, b u t it has been skilfully draw n, an d re stricts th e use of alcohol to an ex te n t which will seriously h a n d i
cap a g reat num ber of th e chem ical in d u stries and p ractically p rev en t th e developm ent of others. T he zeal of th e p ro h ib itio n ist has led him to ignore com pletely th a t section of th e basic law , T itle I I I , which seeks to encourage th e developm ent of th e m an u factu re of in d u strial alcohol an d to facilitate its d istrib u tio n .
I t to o k m any years to educate our legislators to th e necessity of alcohol as a sine qua non in m any lines of in d u stry , b u t th e good w ork was finally accom plished.
M an u factu re began on a large scale and th e needed industries sprang up. Now th e whole stru c tu re , b u ilt in good faith , seems th re a te n e d , ju s t a t a tim e when P resid en t H ard in g is urging th a t a closer and m ore sy m p ath etic relationship betw een governm ent and business should exist. Now w hen Congress is showing th e m ost friendly a ttitu d e to w ard s chem icals in general th ere comes a side swipe ag ain st th e m ost im p o rta n t of all chem ical reagents, alcohol.
New laws are n o t needed here. T he w ording of th e A ct is plain. L et th e new ly ap pointed Com m issioner of In te rn a l R evenue call to his aid rep resen tativ es of th e in d u stries to advise w ith him a b o u t th eir needs and difficulties. He can secure th e ir w holehearted cooper
atio n . T here is o p p o rtu n ity here for th e creation of th a t sy m p a th e tic relationship betw een governm ent an d business for which th e P resident pleads.
504 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 13, No. 6
ORIGINAL PAPERS
The Alkylation of Aromatic Amines by H eating with Aliphatic Alcohols
By Arthur J. Hill and John J. Donleavy
De p a r t m e n t o f Ch e m is t r y, Ya l e Un iv e r s it y, Ne w Ha v b n, Co n n e c t ic u t
1,2,3
I t was shown in a recent p u b licatio n 4 th a t th e fo rm a
tion of diethylaniline, CeHjNCCjHs)», by th e in teractio n of aniline hydrochloride an d eth y l alcohol could be prom oted to a considerable degree by certain cataly sts, am ong which th e tw o following com binations were found to be th e m ost active:
Sodium brom ide Sodium brom ide -
C alcium chloride C opper powder
C upric chloride
T he present investigation is an extension of. this problem to th e toluidine series, an d com prises tw o dis
tin c t phases, nam ely,
1—The action of ethyl alcohol upon the hydrochloridcs of 0-, in-, and ¿»-toluidine.
2—The action of «-butyl alcohol upon the hydrochlorides of aniline, and 0-, m-, and /»-toluidine.
T he cataly sts which were found efficient in th e alkyl- ation of aniline hydrochloride w ith eth y l alcohol have likewise prom oted alk y latio n in this new series of ex
perim ents. F u rth erm o re, th e experim ental results have an im p o rta n t bearing, on th e one h an d , as regards th e com parative a c tiv ity of eth y l an d b u ty l alcohol, an d on th e other, respecting th e sp atial influence of nuclear su b stitu en ts on th e ease of alk y latin g arom atic am ines.
As pointed o u t in th e previous p u b licatio n ,5 th e n a tu r e of th e p ro d u ct resulting from th e alk y latio n of an aro m a tic am ine w ith alcohol is conditioned, in p a r
ticu lar, by tw o factors, nam ely, th e tem p e ra tu re of th e reaction, an d th e presence of certain catalysts.
Influenced by these factors, th e reaction m ay proceed in one of tw o directions, as represented by E q u atio n s
1 and 2.
NHjHCl NHC2H5 N (C ,H s)2
CsH 5OH
>.
NHjHCl CjHsOH
>
C Ä C2H 5
W ith regard to th e effect of tem p eratu re, it appears th a t there is a favorable one a t, or below which, nitrogen alk y latio n predom inates, an d above w hich nucleus su b stitu tio n is facilitated. This tem p e ra tu re is highest w ith m ethyl alcohol and is ap p aren tly low ered in p ro portion to th e com plexity of th e alcohol molecule.
T he action of b u ty l alcohol upon aniline hydrochloride
1 Received F e b ru a ry 26, 1921.
3 “ R esearches on Amines, I X ." T h e previous papers of th is series, with th e exception of V II, T h i s Jo u r n a l, 12 (1920), 636, h a v e been published in th e Journal o f the Am erican Chemical Society.
* T h is p a p er is co n stru cted from a d isse rta tio n presen ted b y Jo h n J.
D o n leav y to th e F a c u lty of th e G ra d u a te School of Y ale U n iv ersity , 1920, in can d id acy for th e D egree of D octor of P hilosophy. (A. J . H.)
4 “ Researches on Amines, V II.”
* Loc. cit.
has recently been in v estig ated by Reilly and Hickin- b o tto m ,1 w ith p articu lar regard to th e factors affecting nucleus su b stitu tio n . T hey have shown th a t the product obtained by h eatin g th is sa lt w ith b utyl al
cohol a t 200° is,2 q u a n tita tiv e ly speaking, a m ixture of th e secondary and te rtia ry bases, whereas a t 240° to 200° th e p ro d u c t3 is chiefly />-«-butylam inobenzene (I).
NH,.HC1 NH.CjHs.HCl NHo.HCl
C A O H
>■
Som ew hat sim ilar results were also obtained with /»-toluidine hydrochloride4 and b u ty l alcohol.
Reilly an d H ickinbottom 5 have subjected th e factors underlying th e in tram olecular rearran g em en t of p - n -
butylam inobenzene to a very th orough investigation, and conclude th a t th is rearran g em en t of alkylaryl- am ines is conditioned b y th e presence of substances which are capable of uniting w ith am ino groups. For example, HC1, ZnCl2, CoCl2, and C dCl2 g reatly facili
ta te th is reaction, while com pounds such as CaSCU, N aC l, C aC l2, and S i0 2 are su b stan tially inactive.
C upric chloride is sta te d to be slightly active. iV-butyl- aniline m ay be heated for several hours a t 240° to 260° w ithout suffering rearran g em en t, w hereas the in tro d u ctio n of th e above-m entioned cataly sts will prom ote intram olecular rearran g em en t to th e extent of 50 per cen t or more, in 7 to 8 hrs. In th e light of these observations it is im p o rta n t to note th a t our m ost efficient cataly tic m ixture for te rtia ry amine form ation is composed of C aC l2, N aB r, an d CuClj, the first tw o of which are inactive w ith respect to pro
ducing nucleus su b stitu tio n , an d th e la st nam ed, active to a sm all degree only. F u rth e r, in the in teractio n of aniline hydrochloride and eth y l alcohol we observed6 th a t ZnCl2 functioned m uch less favorably as a cataly st of nitrogen alkylation th a n C aC l2. Our results are therefore decidedly in accord w ith those of Reilly and H ickinbottom .
T he la tte r have fu rth er co n trib u ted d a ta bearing on th e com parative tendency for rearrangem ent of m ethyl- an d «-butylaniline, in which it seems evident th a t th e la tte r is far more prone to undergo th is reac
tion th a n th e form er, in th e presence of th e catalysts previously referred to.
T he object of our investigation has been prim arily to stu d y the factors productive of th e m axim um yield of th e te rtia ry bases in th e action of eth y l and «-butyl
> J . Chem. Soc., 117 (1920), 103.
5 Ibid., 113 (1918). 102.
2 Ib id , 113 (1918), 976.
* Ibid.. 113 (191S), 976.
* Ib id ., 117 (1920), 103; Chem. N ews, 119 (1919), 101.
* Loc. cit.
June, 1921 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 505 alcohols upon th e hydrochlorides of aniline and th e
isomeric toluidines. This problem has therefore in volved an investigation of th e conditions prom oting a maximum tran sfo rm atio n of A to C, w ith a m inim um production of B on th e one h an d , and D on th e other.
N H , N H R N R 2 N H R
0
(A)- 0
(B)- 0
(C)- Q
(D)We have observed th a t th re e factors have a predom i
nant influence on th e form ation of th e te rtia ry base, C, nam ely, th e co n centration of th e alcohol, th e nature of th e cataly st, and th e te m p eratu re of th e reaction. I t has h ith e rto been com m on p ractice1 to utilize tw o or th ree moles of alcohol in th e in teractio n of amine hydrochlorides w ith alcohols for th e p ro d u c
tion of te rtia ry bases. T he utilization of a large ex
cess of alcohol, te n m olecular proportions, g reatly de
creases secondary am ine form ation, B. W ith regard to the use of cataly sts, we have found th a t th e com bined influence of calcium chloride, sodium brom ide, and cupric chloride, to g eth er w ith th e hydrogen chlo
ride of the salt, facilitates th e tran sfo rm atio n of A to C.
However, these sam e cataly sts, p a rticu larly th e last named, above a tem p e ra tu re which is ap p a re n tly definite for each alcohol-am ine m ixture, in itia te also the above-described nitrogen to carbon rearrangem ents.
This critical tem p e ra tu re we have found to be 175°
to 180° in all of th e alkylations herein described, th e extent of te rtia ry am ine form ation, however, being considerably less in every case where b u ty l alcohol was used, as com pared w ith eth y l alcohol. This is shown in th e following tab le:
A niline ^ -T o lu id in e wi-Toluidine o-Toluidine P e r c e n t P e r c e n t P er c e n t P e r c en t
E thyl a lc o h o l 95 9 1 .6 9 0 .2 5 76
Butyl a lco h o l 75 7 7 .4 7 9 .8 4 8 .5
In other words, th e te m p e ra tu re a t which nitrogen to carbon rearran g em en t sets in w ith b u ty l alcohol is apparently lower th a n th a t of eth y l alcohol, and al
though te rtia ry am ine form ation m ight h ypothetically be increased a t te m p eratu res higher th a n 180°, th e possible resu lt is nullified by th e in itia tio n of th e re
action typified by th e tran sfo rm atio n of C to D.
The in teractio n of alcohols an d th e derivatives of aniline presents a m ore com plicated problem th a n is involved w ith th e 'p ro to ty p e of th e series. ,I n th e la t
ter case, th e entering group need only be considered, whereas, w hen derivatives of aniline, such as th e iso
meric toluidines, are em ployed, th e o rien tatio n of th e methyl groups in th e benzene nucleus m arkedly affects the re a c tiv ity of th e am ine in question. T h a t ortho substituents in h ib it th e re a c tiv ity of ad ja c e n t nucleus groups has long been recognized. We should th e re fore expect th e alk y latio n of o-toluidine hydrochloride to present certain anom alies, as com pared w ith th e reactivity of th e m eta and p a ra derivatives. - This has been found to be rem ark ab ly th e case in th e present investigation. W hile th e p - a n d »»-toluidines could be eth y lated or b u ty la te d to su b stan tially th e sam e
1 Th i s Jo u r n a l, 12 (1 9 2 0 ), 638.
degree, th e ex ten t of te rtia ry am ine form ation was 14 to 16 per cent less in th e case of o-toluidine and eth y l alcohol, and as m uch as 29 to 31 per cent less w hen b u ty l alcohol was used as th e alkylating agent.
This is by no m eans th e first observation concerning th e steric influence1 of o rth o su b stitu e n ts upon th e alk y latio n of am ines. H ow ever, so far as th e w riters have been able to ascertain, th e present observ atio n on th e steric influence of ortho su b stitu e n ts upon th e reaction betw een alip h atic alcohols an d th e salts of aryl am ines is th e first of th is n a tu re to be recorded.
Q uite recently, R eilly2 in v estig ated th e action of w -butylchloride upon o-toluidine, and was able to ob
ta in only m ono-butyl-o-toluidine. In an effort to p re pare th e te rtia ry am ine he digested m ono-w-butyl- o-toluidine w ith an excess of «-butylchloride for 10 days. E ven under these conditions he was unable to obtain th e te rtia ry base.
E X P E R IM E N T A L
T he alkylations described below were all carried o u t in an iron autoclave of 1.7 lite rs’ capacity. T he la tte r was equipped w ith th e usual pressure gage and th e r
m om eter well, and p ro tected from corrosion by m eans of a glass inset. T he location of th e therm o m eter well was such th a t th e tem p eratu res recorded were those of th e v apor phase. T he autoclave was heated in a b a th of cottonseed oil.
T he m ethod of isolating th e alkylation pro d u cts in each experim ent was as follows: T he unchanged al
cohol was first rem oved by distillation under dim in
ished pressure. By th is m eans very econom ical re covery could be m ade of th e large excess of alcohol re quired to effect com plete alkylation. T he residue was th e n m ade strongly alkaline w ith sodium hydroxide, an d th e liberated bases distilled w ith steam . The am ines were sep arated from th e aqueous d istillate by eth er ex tractio n and dried over anhy d ro u s sodium sul
fate. In th e case of th e butyltoluidines, how ever, th e am ines were n o t steam -distilled b u t ex tracted directly from th e alkaline solution w ith ether, by reason of th e fa c t th a t th e aro m atic b u ty l am ines steam -distil a t a m uch slower ra te th a n th e corresponding eth y l deriv a
tives. A fter rem oval of th e eth er, th e oils were fractio n ally distilled a t atm ospheric pressure, th e distillates being collected a t 2° intervals.
T h e ex ten t of te rtia ry am ine form ation in each ex
perim ent was determ ined by an estim ation of th e acetylizable m aterial in th e reaction p ro d u ct (see previous paper for details), and th e result calculated in term s of th e m ono-alkylated amine.
S Y N T H E S IS O F T H E IS O M E R IC D IE T IIY L T O L U ID IN E S
R o m b u rg h 3 p repared diethyl-o- an d -/»-toluidine by th e in teractio n of eth y l alcohol an d th e corresponding p rim ary bases in th e presence of hydrochloric acid.
I n order to effect alk y latio n he heated his reaction m ixtures a t 200° to 220° for 48 hrs. Since th e p rim ary purpose of his investigation was th e stu d y of th e ni-
> Ber.. 5 (1S72), 707; 8 (1875), 61; 18 (18S5), 1824 ; 32 (1899), 1401;
33 (1900), 3 4 5 ;3 3 (1900), 1967; J . prakl. Chem., 65 (1902), 252; A n n ., 346 (1906). 128.
» J . Chem. Soc., 113 (1918). 974.
* Rec. trav. chim., 3 (1 8 8 4 ). 392.
506 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 13, No. 6 tra tio n of these bases, he ap p aren tly devoted b u t little
a tte n tio n to th e ir synthesis. This brief reference is th e only record in th e lite ra tu re concerning th e action of eth y l alcohol upon th e hydrochlorides of o- and
¿-toluidine. However, th e p rep aratio n of diethyl-o- and -¿-toluidine from th e p rim ary am ine hydrobro- mides or hydriodides an d eth y l alcohol is recorded by Stadel,1 who states th a t yields of 90 per cent or b e tte r are ob tain ed a t 150° an d 125°, respectively. Mono- as well as diethyl-o- and -¿-toluidines have also been prepared by alk y latio n of th e p rim ary bases w ith alkyl halides.2
So far as th e w riters are aw are, th e re is no available inform ation concerning th e action of eth y l alcohol upon »¡-toluidine hydrochloride. B eilstein3 refers to th e work of S tadel4 for th e p rep aratio n of diethyl- w-toluidine, b u t th e la tte r appears to hav e p repared only th e ortho and p a ra derivatives. F u rth e r, th e p a te n t which covers S tadel’s alk y latio n procedure does n o t designate th e prep aratio n of diethyl-m -tolu- idine, although th e o rth o an d p a ra d erivatives are specifically m entioned. W einburg5 accurately d e te r
m ined th e boiling p o in t of th e mono- an d dieth y lated toluidines, including diethyl-w -toluidine, b u t did not sta te how th e bases were prepared. I n fact, th e only direct inform ation respecting th e p re p aratio n of this te rtia ry base is to be found in a paper by G oldschm idt an d Keller,* who, giving no details, m erely m ention th e fact th a t th e y prepared this com pound by S tad el’s general m ethod.
T he w riters have now carefully stu d ied th e factors affecting te rtia ry am ine form ation in th e in teractio n of ethyl alcohol an d th e isom eric toluidines. T he results of these experim ents are em bodied in T ables I, I I , and I I I .
D IE T H Y L -/> -T O L U ID IN E
T he resu lts which were obtained by h eatin g ¿-to lu idine hydrochloride w ith ten molecules of eth y l alcohol are recorded in E x p t. 1, T able I. T h e p ro d u ct of this reaction distilled for th e m ost p a rt w ithin a range of 4 ° an d contained b u t 9.45 per cent secondary amine.
T he addition of copper pow der an d sodium brom ide (E xpt. 2) to th e reaction m ixture increased th e form a
tion of th e te rtia ry base, while th e second set of c a ta lysts (E xpt. 3) produced no positive effect. T he best conditions for th e form ation of diethyl-/>-toluidine are therefore represented in E x p t. 2.
In order to isolate pure diethyl-/>-toluidine, th e crude oil was heated for 3 hrs. w ith an equal w eight of acetic anhydride. T he resulting p ro d u ct was th e n fractio n ally distilled a t atm ospheric pressure. T he te rtia ry base was obtained as a pale yellow oil which boiled a t 230° a t 755 mm. T his resu lt is in accord w ith the previous observations of W einberg,7 who rep o rted a boiling p oint of 229° for th is am ine.
1 Ber„ 16 (1SS3), 29; D . R . P . 21,243 (1883).
* A n n ., 93 (1855), 313; A m . Chem. J ., 7 (1885), 119.
I Vol. I I , 477.
* Loc. cit.
« B e r 25 (1S92), 1613.
« Ibid., 35 (1902). 3540.
* Loc. cit•
Table I—Diethyl-£-Toluidinb
(100 g. /»-toluidine hydrochloride; 320 g. ethyl alcohol; time, 8 hrs.;
temperature, 175°-180*)
„ Expt. 1 Expt. 2 Expt. 3
Catalysts:
Sodium bromide, grams... . . 10 10 Calcium chloride, grams... . . . . 10 Cupric chloride, grams. ... .. . . 5 Copper powder, grams... .. 5 Total oil, grams... 106 107 103 Acetylizable portion of oil, per cent 9.4 7.9 9.4 Calculated tertiary base, per cent... 90.6 92.1 90.6 Distillation. Temperature
224°-226°, cc... 2 . . 1 226°-22S°, cc... 68 28 42 228°-230°, cc... 38 69 51 230°-232°, cc... 13 7
DIETHYL-W-TOLUIDINE
A p r o d u c t c o n t a in in g 1 1 .8 p e r c e n t a c e t y liz a b le m a te r ia l w a s f o r m e d b y h e a t i n g w i-to lu id in e h y d r o c h lo r id e w it h t e n m o le c u le s o f e t h y l a lc o h o l ( E x p t . 1, T a b le I I ).
T h e d e g r e e o f a l k y l a t io n w a s s l i g h t l y lo w e r in t h is ca se t h a n t h a t o b t a in e d w h e n t h e p a r a s a lt w a s tr e a te d u n d e r s im ila r c o n d it io n s . T h e p r o p o r t io n o f te r tia r y b a s e in t h e r e a c t io n p r o d u c t w a s r a is e d b y t h e u s e of c a t a ly s t s ( E x p t . 3 ) . O n t h e o t h e r h a n d , i t is o f in te r e s t t o n o t e t h a t c o p p e r p o w d e r ( E x p t . 2 ) e x e r t e d a n in- h i b it i v e a c t io n . I t is d iffic u lt t o e x p la in t h i s a p p a r e n t a n o m a ly , s in c e in a ll p r e v io u s a lk y l a t io n s i t s u s e h as p r o v e d b e n e fic ia l.
T h e b e s t e x p e r im e n t a l c o n d it io n s ( E x p t . 3) fo r th e p r e p a r a t io n o f d ie t h y l - w - t o l u i d i n e w e r e t h e r e f o r e p r o d u c t iv e o f o ils w h ic h c o n t a in e d a b o u t 90 p e r c e n t of t h e t e r t ia r y b a s e . T h is fig u r e is a b o u t 2 p e r c e n t low er t h a n t h e r e s u lt s o b t a in e d w i t h t h e p a r a b a s e , a n d 5 per c e n t lo w e r t h a n t h o s e o b t a in e d w i t h a n ilin e .
A p r o c e d u r e s im ila r t o t h a t a p p lie d i n t h e c a s e o f th e p a r a d e r iv a t i v e s w a s u s e d fo r t h e is o l a t io n o f d ie th y l- w - t o lu id in e . T h e l a t t e r w a s t h e r e b y o b t a in e d a s a lig h t : y e llo w o il w h ic h b o ile d a t 2 3 2 ° u n d e r 7 5 5 m m . p r e s s u r e . W e in b e r g 1 r e p o r t e d a b o ilin g p o in t o f 2 3 1 .5 ° fo r t h i s c o m p o u n d .
Table II—DiETnYL-m-ToLuiDiNE
(50 g. m-toluidine hydrochloride; 160 g. ethyl alcohol; time, 8 hrs.;
temperature, 175°-180°)
Expt. 1 Expt. 2 Expt. 3 Catalysts:
Sodium bromide, grams... .. 5 5
Calcium chloride, grams... . . . . 5 Cupric chloride, grams... .. . . 2.5 Copper powder, grams... .. 2.5
Total oil, grams.. ... 55 47 48 Acetylizable portion of oil, per cent.. .. 11.8 13.7 9.75 Calculated tertiary base, per cent 88.2 86.3 90,25 Distillation. Temperature
226°-228°, cc... 2 7 13
228°-230°, cc... 16 19 17
230°-232°, cc... 20 9 8
2320-234°, cc... 4 4 4
234°-236°, cc... 4 4 4
236°-238°, cc... 4 4 2
DIETHYL-0-TOLUIDINE
T h e s t e r ic in f lu e n c e o f o - s u b s t it u e n t s u p o n th e a l k y l a t io n o f a m in e s is i n t e r e s t i n g l y d e m o n s t r a t e d in t h e in t e r a c t io n o f o - t o lu id in e a n d e t h y l a lc o h o l. W h e n t e n m o le s o f t h e la t t e r w e r e h e a t e d w i t h 0- t o lu id in e h y d r o c h lo r id e ( E x p t . 1, T a b le I I I ) , t h e p r o d u c t c o n t a in e d 32 per cent of the secondary base. I t h a s a lr e a d y b e e n s h o w n t h a t t h e a l k y l a t io n o f t h e m e t a a n d p ara is o m e r s b y t h i s m e t h o d y i e l d s a p r e p o n d e r a n c e o f th e t e r t ia r y a m in e . I n f a c t , in n e it h e r c a s e d id t h e a c e t y l
iz a b le p o r t io n o f t h e o il e x c e e d 12 p e r c e n t . T h e re s u lt w it h o - t o lu id in e t h e r e f o r e o ffe r s a s t r ik in g c o n tr a s t.
T h e e f fe c t o f t h e c a t a ly s t s ( E x p t s . 2 a n d 3 ) , h o w e v e r , w a s m o r e a p p a r e n t w it h t h i s b a s e t h a n w it h t h e m e ta
* Loc. cit.
June, 1921 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 507 and p ara derivatives. T he best resu lts were obtained
by th e use of cupric chloride, sodium brom ide, an d calcium chloride (E x p t. 3). T h e oil contained 24 per cent of th e m ono-alkylated base. E ven this, however, is quite inferior to th e degree of alk y latio n ob tain ed when th e isom ers were sim ilarly tre a te d .
Ta b l e I I I — Di e t h y l-o- To u h d i n e
(100 g . o -to lu id in e h y d r o c h lo r id e ; 3 2 0 g . a lc o h o l; tim e , 8 h rs .) Ex p t. 1 Ex p t. 2 Ex p t. 3 Ex p t.4 1
Sodium brom ide, g ra m s ... 10 10 5
C alcium chloride, g ra m s... 10 5
C upric chloride, g ra m s ... 5 2 .5
C opper pow der, g ra m s ... ‘ 5
Tem perature, ° C ... 175 175 175 200 Total oil, g ra m s... ... 87 92 91 40 Acetylizable p o rtio n of oil, p e r c e n t ... 3 2 .3 2 8 .6 24 3 9 .9 C alculated te rtia ry base, p er c e n t . . . . 6 7 .7 7 1 .4 76 60 .1 D istillation. T e m p e ra tu re 2 0 6 °-2 1 0 °, c c ... 5 5 6 210°—214°, c c ... 65 67 64 2 1 4 °-2 1 8 °, c c ... 15 19 15 *i 2 1 8 °-2 2 2 °, cc ... 7 7 8 2 222°—226°, c c ... 3 2 226°—230°, c c ... 7
2 3 0 °-2 3 4 °, c c ... 8
2 3 4 °-2 3 8 °, c c ... 6
2 3 8 °-2 4 2 °, c c ... 7
1 O ne-half th e usual a u toclav e charge used in th is experim ent. In order to ascertain th e effect of higher te m p e ra tures, an experim ent was carried o u t a t 200° C. w ith most efficient cataly sts. T his m odification of condi tions (E x p t. 4) greatly increased th e p ro p o rtio n of acetylizable bases. I t is q u ite ev id en t from th is o b servation th a t intram o lecu lar rearran g em en t will ta k e place to some ex ten t a t te m p e ra tu res of 200° C. Owing, therefore, to th e inhibitive effect of th e ortho substituent, th e best experim ental conditions failed to produce a p ro d u ct containing m ore th a n 76 per cent diethyl-o-toluidine. The p u re te rtia ry base was isolated from th e reac tion m ixtures by th e use of th e m ethod previously d e scribed for th e p rep aratio n of th e m eta and p a ra isomers. It was obtain ed as a p ractically colorless oil which boiled a t 206° to 208° C. a t 755 m m . S tad el,1 who has previously p repared th is base, sta te s th a t it boils a t 208° to 209°. D I-7 I-B U T Y L A N IL I N E As sta te d above, th e action of « -b u ty l alcohol upon aniline has recently been in v estig ated by R eilly an d Us co-workers. T heir investigations, how ever, are of particular value in th e ir inform ation respecting th e intram olecular rearran g em en t of «-butylaniline, while their observations w ith regard to th e degree of nitrogen alkylation b y th is m ethod are w holly q u alitativ e. The w riters have therefore sought to establish th e ex perim ental conditions pro d u ctiv e of th e m axim um yield of di-w-butylaniline. T he resu lts of these in vestigations are given in T able IV. W hen aniline hydrochloride was h eated a t 175® with ten moles of « -b u ty l alcohol (E x p t. 1, T able IV ), the alk y lated p ro d u ct contained b u t 51 per cen t di- butylaniline. I t is in terestin g to n o te th a t u nder similar conditions eth y l alcohol yielded an oil con taining 88 per cen t diethylaniline. T h e difference in the re a c tiv ity of these tw o alcohols is plainly evident from these observations. The effect of in tro d u cin g th e ca ta ly tic m ixture (Expt. 2) was q u ite m arked. T he yield of d ib u ty l- aniline was raised from 51 to 75 per cent. T h e range 1 hoc. cit. of d istillatio n of th is oil, com pared w ith th a t obtained in E x p t. 1, indicates th e considerable increase in th e am o u n t of te rtia ry base produced b y th is change of procedure. In order to ascertain w hether or n o t 175° was th e o p tim um te m p eratu re, an experim ent was carried o u t u nder th e favorable conditions of E x p t. 2, th e te m p eratu re, however, being raised to 200°. As a result, th e am o u n t of d ib utylaniline was decreased a b o u t 5 per cent. T his was due, no d o u b t, to an in tra m olecular rearrangem ent, in which nuclear alk y lated am ines were produced in accordance w ith th e following equation: CtHs.NH.CiH, — >- ^-NHi.CiII(.C1IIs R eilly utilized tem p eratu res of 240° to 260° in order to o b tain ¿-n-butylaniline, b u t th e results of E x p t. 3 suggest th a t alk y latio n of th e nucleus, although n o t pred o m in an t, m ay ta k e place a t 200° C., or even lower. We did n o t operate a t te m p e ra tu res lower th a n 175°, since th e autoclave pressure, which is an im p o rta n t facto r, decreases m aterially below th is tem p eratu re. T he m ost favorable conditions for th e form ation of d ib u ty lan ilin e are therefore show n in E x p t. 2. E ven these, how ever, produce a te rtia ry am ine form ation which is 20 per cen t below th a t o b tain ed w ith eth y l alcohol. T he wide difference in th e re a c tiv ity of th e tw o alcohols m ay be seen from inspection of th e follow ing tab le: Co m p a r is o n o p Et h y l a n d « - Bu t y l Al c o h o l s i n Th e i r Re a c t io n w it h An i l i n e Hy d r o c h l o r id e E th y l Alcohol n -B u ty i Alcohol P e r c e n t P e r c en t Alcohol (ten m o les)... 88 51 Alcohol (ten moles a n d c a ta ly s ts )... 95 7 5 .5 T h e ab o v e p ercen tag es refer to th e a m o u n t of tertiary am ine in th e re a ctio n p ro d u cts. P ure di-n-butylaniline was prepared by th e following procedure: F ifty gram s of th e crude am ine, containing a b o u t 25 per cen t of th e secondary base, were h eated for 3 hrs. w ith a n equal w eight of acetic anhydride. T he resulting p ro d u ct was rep eated ly distilled in order to sep arate th e te rtia ry base from th e acetobutylaniline. A fter careful fractio n atio n , di-»-butylaniline was ob ta in e d as a lig h t yellow oil, which boiled a t 262° to 264° u nder 755 m m . pressure. R eilly1 rep o rted th e boiling p o in t of th is com pound as 260° to 263° u nder 767 m m . pressure. An a l y s is(K jeld ah l) P e r c en t C alcu lated for C hH m N : N ... 6.86 F o u n d : N ... 7 .0 0 Ta b l e IV — Di- « - Bu t y l a n i h n b (50 g. aniline hy d ro ch lo rid e; 285 g. n -b u ty l alcohol; tim e , 8 hrs.) Ex p t. 1 Ex p t. 2 Ex p t. 3 C ataly sts: Sodium brom ide, g ra m s ... 5 5 C alcium chloride, g ra m s... 5 5 C u p ric chloride, g ra m s ... 2 .5 2 .5 T e m p e ra tu re , 0 C ... T o ta l oil, g ra m s... 175-180 200 ,. 47 53 51 A cetylizable p o rtio n of oil, p er c e n t.. . . , . 49 24 3 0 .3 C alcu lated te rtia ry base, p er c e n t... 51 75 6 9 .7 D istillatio n . T e m p e ra tu re 244 °-2 4 8 , c c ... 7
2 4 3 °-2 5 2 ‘\ c c ... 15 4 2 5 2 °-2 5 6 °, c c ... 9 4 2 5 6 °-2 6 0 °, c c ... 7 13 8 2 6 0 °-2 6 4 °, c c ... 0 10 15 2 6 4 °-2 6 8 °, c c ... 13 13 26S0-2 7 2 ° , c c ... 9 5 272°—276°, c c ... 4 3 2 76o-2 8 0 ° , c c . ... 1 _________280o- 284°, c c ...
i J . Chem. Soc., 1 1 3 (1918), 99.
