of their velocities of hydrolysis w ith those of the corresponding ethyl arylcarboxylates.
L.D em Iin y (Rec. tra v . ehira., 1931, 5 0 , 60— 71).— Tho following eth y l arjd su lp h o n ates have been p rep ared b y th e actio n of sodium eth o x id e on th e a p p ro p ria te sulphonyl chloride in d ilu te alcoholic solution : eth y l benzene-, o-, b. p. 160— 163°, m . p . 15°, m -, m. p. 42°, a n d
p-,
m . p. 92°, -nitrobenzene-, a n dp-toluene-sulphonatea. I n general, th e velocity of hydrolysis of th e sulphonic esters in 30 v o l.-% alcohol in 0-001JY- alkaline solution is a b o u t ono te n th t h a t of th e corre
sponding carboxylic ester. W ith sulphonic esters th e effective hydro ly sin g ag e n t is considered to be w ater a n d th e velocity depends only slightly on th e co n ce n tra tio n of alkali used. T h e m ean values for th e unim oleeular velocity coefficient k x 104 in 30%
alcohol a t 25° for th e above sulphonic esters are, respectively, 3-S, 7 5 ,2 4 ,2G, a n d 1-9 (alk alin ity 0-001—
0-008JV), th e v alues of th e bim olecular coefficient k for th e corresponding ca rb o x y lates being 0-46, 1-23, 11-4, 19-0, an d — , respectively (alkalinity 0-003—
0-005AT). In tro d u c tio n of a n itro-group in th e m- or p-positions has a sim ilar accelerating effect in b o th series, b u t in th e o-position its effect is sm all in th e case of th e carboxylic esters, w h ilst i t has a pow erfully accelerating influence in th e sulphonic ester series.
J . W . Ba k e r. A r y ls u lp h o n a lk y la m id e s . L. De m e ny (R e c . tra v . chim ., 1931, 50, 51— 59).— B y th e actio n of a n alcoholic solution of th e ap p ro p ria te am ine on various ary lsulphonyl chlorides a series of ary lsu lp h o n alk y l
am ides lias been p rep ared , th e following being new : benzenesulphon-n-hexylamide, m . p. 17°, a n d -n- heptylamide, m. p. 20°; p-bromobenzencsulphon-n- amylamide, m. p. 55° (not sharp), -n-hexylamide, m . p. 55°, an d -n-heptylamide, m . p. 65°; p -toluene- sulphon-n-bulylamide, m. p. 43°, -n-amylamide, a colour
less oil, -n-hexylamide, m . p . G2°, a n d -n -heptylamide, m . p . 4 5 °; mesitylenesulphon-n-propylamide, m . p . 54°, -n-butylamide, m . p . 44°, -n-amylamide, m . p . 42°, -n-hexylamide, m . p. 64°, -n-heptylamide, m . p.
45°. T he m . p. of these d eriv ativ es a n d those p re viously p re p ared (A., 1930, 81) are in general agree
m e n t w ith th e various laws connecting m. p . an d co n stitu tio n , a m inim um value occurring in th e case of th e M-amylaminc d eriv ativ es. J . W . Ba k e r.
D ito ly l s e r i e s . I. A . An g e l e t t i [w ith A . Br a m b il l a] (G azzetta, 1930, 60, 967— 974).—
2-Iodo-2'-nitro-4:: i'-dim ethyldiphenyl (o-iodo-o'-nilro- ditolyl), m . ]). 83—84°, p re p ared from 2-nitro-2'- a m in o -4 : 4'-d im eth y ld ip h en y l (cf. M ascarelli and G a tti, A ., 1930, 205) by w ay of th e diazo-com pound, is accom panied b y a sm all q u a n tity of ditolylcnc- iodonium iodide ('?) a n d , as in th e p re p a ra tio n of th e following com pounds, b y 4 : 4 '-dim ethyldiphenylene oxide (cf. N iem entow ski, A ., 1902, i, 21). I t seems t h a t decom position of th e diazo-nitro-com pound gives first th e 2'-n itro -2-hydroxy-com pound, w hich loses n itro u s acid to form th e dim ethyldiphenylene oxide.
2-Bromo-, m . p . 73— 74°, an d 2-chloro-2f-n itro-i : 4 '- dimethyldiphenyl, m . p. 85— 86°, w ere also p rep ared , b u t a tte m p ts to o b ta in 2 '-n itro -2 -h y d ro x y -4 : 4 '- dim eth y ld ip h en y l w ere unsuccessful. T. H . Po p e.
H a lo g e n s u b s t i t u t i o n . II . P . Pf e i f f e r a n d P . Sc h n e i d e r (J . p r. Chem., 1931, [li], 1 2 9 , 129—
144).— Coloured u n sta b le carbonium salts, sim ilar to those form ed from brom ine v a p o u r an d auxochrom e- s u b s titu te d aa-d iary leth y len es (cf. A ., 1928, 633), are also given b y th e p a re n t h ydrocarbons. T he follow
ing hyd ro carb o n s were ex am ined as to (a) colour of solutions in sulphuric acid (form ation of a carbonium su lp h ate) an d (b) colour produced by brom ine v ap o u r
(a perbrom ide), a n d were co n v erted by th e th eo retical a m o u n t of brom ine in so lution in to th e m ono- and di-b ro m o -su b stitu tio n p ro d u cts, w hich w ere exam ined sim ilarly : diphenyl- a n d di-p-tolyl-ethylene, no re a c tio n ; «.a-dinaphthylethylene, m . p. 107°, from m agnesium n a p h th y l brom ide a n d e th y l a c e ta te and su b seq u en t d eh y d ra tio n of th e carbinol, m . p. 146°, form ed, (a) deep m alachite-green, (6) in d is tin c t r e d ;
$-bromo-'m-dinaphthylcthylene, m. p. 148°, (a) bluish- green, (b) re d d ish -b ro w n ; tetrabromo-aa-dinaphthyl- ethylene, m . p. 69— 70°, from th e h y d ro carb o n and excess brom ine in chloroform , (a) in ten se g rass-green;
p -d ip h en y ly lp h eu y lcth y len e, m. p. 94— 95°, from th e corresponding k eto n e a n d m agnesium m e th y l iodide (cf. Schlenk a n d B ergm ann, A ., 1928, 1031), (a) cherry-red, (5) g rass-g re e n ; $-bromo-v.a.-p-diphenylyl- phenyletliylene, m . p. 162°, (a) reddish-violet, (6) d a rk v io let; $$-dibromo-v.v.-p-diphcnylylphenylethylenc, m . p.
155°, (a) re d d ish -v io le t; di-p-diphenylylethylene, m . p.
2 1 1°, (a) reddish-violet, (6) deep g re e n ; ¡i-bromo- cLx-di-p-diphenylylethj/lene, m . p. 187— 188°, (a) green, changing to bluish-green on w a rm in g ; w ith oleum deep blue, a n d (b) re d d ish -b ro w n ; $$-dibromo-<m-di- p-diphetiylyleihylene, m . p. 194— 195°, aa-di-p-di- phenylyl-Aa-propene, m . p. 165— 166°, (a) deep reddish- violet, (6) deep g re e n ; $-bromo-<x<x-di-p-diphenylyl- Aa-propene, m. p. 150— 152°, (a) bluish-violet on w arm ing, (6) g re y isli-b la c k ; a-phenyl-$$-di-p-di- phenylylethylene, m . p. 192— 193°, (a) violet, (b) grass- g re e n ; </.-bromo--x-phenyl-^i>-di-p-diphenylyletliyUne, m. p. 201—202°, (a) deep bluish-green w ith oleum.
A n a tte m p t to produce aa-d in ap h th y l-p -p h en y leth y l- ene from p h e n y leth y l a c e ta te a n d m agnesium n a p h th y l iodide yielded only d iphenylacetoacetic ester.
E . Ho p k i n s. 2 - P h e n y l- l : 1 - d im e th y lin d e n e . J . C. Ea r land C. A. Sm y t h e (J. P roc. R oy. Soc. N ew S o u th W ales, 1930, 44, 90— 95).— A lum inium brom ide can be used in th e sam e w ay as alum inium chloride fo r th e rem oval of aro m atic hydrogen (cf. Scholl, A., 1913, ii, 56, 734 ; 1922, i, 258, 261, 331, 336), an d can also be used for th e rem oval of alip h atic hydrogen. T h e in teractio n of alum inium brom ide, trim e th y leth y len e dibrom ide, an d benzene yields 2-phenyl-l : l-dimethylindene, m . p.
51°, b. p. 190— 205°/36— 38 m m ., w hich, according to conditions, is oxidised to p h th a lic acid or o-a-benzoyl- o.-mcthylethylbenzoic acid, m. p. 198°, co n v erted by acetic an h y d rid e in to 3-acetoxy-3-phenyl-4:: 4 -di
methyl-3 : ‘l-dihydrobcnzisopyrone, m. p. 137°. 3-Nitro-2-phenyl-1 : l-dimethylindene, m . p. 139— 140°,
is described. G. Dis c o m b e.
R e d u c tio n of n a p h t h a l e n e b y a l k a l i m e t a l s in l iq u id a m m o n i a . C. B. Wo o s t e r an d F . B.
Sm it h (J. A m er. Chem. Soc., 1931, 5 3 , 179— 187).—
D eterm in atio n s of th e a m o u n t of h ydrogen (or eth an e) evolved w hen th e reactio n m ix tu res from n a p h th a le n e a n d excess of sodium in liquid am m onia are tre a te d w ith am m onium brom ide (or ethyl brom ide) in d icate t h a t 4 a to m s of th e m e ta l p e r 1 mol.
of n a p h th a le n e are consum ed. H ydrolysis of the re s u lta n t sodio-derivative gives 1 : 2 : 3 :4-tetrah y d ro - n a p h th a le n e , in d icatin g t h a t th e sodium ato m s add in th e 1 : 2 : 3 : 4-positions. T his tetraso d io -d eriv ativ e is show n to be ap p ro x im ately th ree q u a rte rs
ainmono-O R G A N IC C H E M IS T R Y . 3 4 1
lysed in solution a t —33-5°, b y d e term in atio n s of th e am o u n ts of sodium peroxide (from th e excess of sodium) a n d n itrite (from sodam ide) form ed w hen th e reaction m ix tu re is oxidised w ith oxygen. P o tassiu m and n a p h th a le n e re a c t in essentially th e sam e m an n er.
The re su lts s u p p o rt W illsta tte r, Seitz, an d B u m m ’s th e o ry (A., 1928, 756) of red u c tio n s using sodium am algam . T hose h y d ro carb o n s, including n a p h th a l
ene, show n b y L ebeau a n d P icon (A., 1914, i, 825, 946) to be reducible b y sodium a n d liquid am m onia, all fu rn ish alk ali m e ta l a d d itiv e com pounds.
H . Bu r t o n. I n t e r a c t i o n of t c v t .- b u ty l c h lo r id e a n d n a p h t h a l ene. W . Gu m p (J. A m cr. Chem. Soc., 1931, 53, 380— 381).— W h en to 'i.-b u ty l chloride (2 m ols.) is heated w ith n a p h th a le n e (1 m ol.) in presence of a small a m o u n t of alum inium chloride, a m ix tu re of two ditevt.-butylnaphthalenes, b. p. 319°, m . p. 82-—
83°, a n d b. p. 320°, m . p . 145— 146°, separable by fractional c ry stallisatio n from alcohol, is ob tain ed . These are p ro b a b ly id en tical w ith th e supposed 1 : 2'- an d 1 : l'-d in a p h th y ls of W egscheider (A., 1884, 1185), o b tain ed d u rin g th e re a c tio n betw een naphthalene an d fsobutyl chloride. A ieri.-butyl- naphthalene could n o t be p re p a re d from equim olecular am ounts of th e re a c ta n ts. H . Bu r t o n.
A n th r a c e n e d e r iv a tiv e s . I I I . E . d e B. Ba r netta n d J . A. L o w (B er., 1931, 6 4 , [A], 49— 56).— I n spite of th e im possibility of a p e n -c o -o rd in atio n , th e derivatives of 1 : 4 -d im eth y lan th racen e resem ble th e corresponding d e riv ativ es of 1 : 4-, 1 : 5-, a n d 4 : 5-di- chloro- a n d ,1 : 5 -diplienoxy-anthracene m uch m ore closely th a n th o se of a n th ra c e n e itself. Since th e assum ption t h a t th e d e p a rtu re from “ norm al anthracene p ro p erties ” is conditioned b y different factors in th e m e th y l a n d ch loro-derivatives ap p ears unjustifiable, th e hyp o th esis of a p e n -c o -o rd in a tio n is considered u n ten ab le in sp ite of th e num erous o b serv ations in its favour.
o -2 : 5-D im ethylbenzoylbenzoic acid, m . p. 149°, prepared from p h th a lic an h y d rid e a n d p -x y len e in presence of alum inium chloride, is reduced b y a c tiv ated zinc d u st, sodium h y d roxide, a n d am m onia to
°-2 : o-dimethylbenzylbenzoic acid, m. p. 136°, converted by hot 80% sulphuric acid in to 1 : 4 -d im eth y l
anthrone, m . p. 116°. 1 : 4-Dimeihylanthranyl acetate, from the a n th ro n e b y p y rid in e a n d acetic an h y d rid e, has m. p. 162°. R ed u ctio n of 1 : 4 -d im eth y lan th ro n e with activated zinc d u s t a n d a m m onia gives 1 : 4-di- methyl-9: 1 0 -dihydroanthranol, m . p. 134°, from w hich 1 : 4-dim ethylanthracene, m . p. 76°, is derived.
Successive tre a tm e n t of 1 : 4 -d im eth y lan th ro n e w ith magnesium m eth y l iodide a n d w ith hydrochloric acid m glacial acetic acid yields 1 : 4 : {)-trimethylcmthracene, m ' J1' 9-Benzyl-1 : 4-dimethylanthracene, m . p.
135°, is c onverted b y brom ine in carb o n disulphide into lO-bromo-O-benzylidene-1 : 4-dimelhyl-0 : 10-di- hydroanthracene, m . p. 180°, from w hich th e corre
sponding 10-piperidino-, m. p. 150°, \0-m ethoxy-,m . p.
118— 119°, an d 10-eik.oxy-, m . p. 130°, -d eriv ativ es are obtained. 10-Bromo-l : 4-dimethylanthrone, decom p, ab o u t 160°, is tran sfo rm ed in to 10-piperidino-] : 4-di- methylanthrone, m . p . 133°, 10-ahilino-l : 4-dimethyl- anthrone, m . p. 192°, 10-methylanilino-l : 4-dimethyl
anthrone, m . p. 179°, 10-p-dimethylaminophenyl- 1 : 4-dimethylanthrone, m . p. 154°, a n d 10-methoxy- 1 : 4-dimethylanthrone, m . p. 76°. 10-B rom o-l : 4- d im e th y la n th ro n e is co n v erted b y benzene a n d a lum inium chloride in to 10-phenyl-l : 4-dimetkyl- anthrone, m . p . 144°, w hich w hen tre a te d successively w ith m agnesium m e th y l iodide a n d hydrochloric acid in glacial acetic acid gives 10-phenyl-l : 4-dimetliyl-O-methylene-O : 10-dihydroanthracene, m . p. 129°, oxidised b y chrom ic acid to 10-phenyl-l : 4 -d im eth y l
a n th ro n e. 10 - Phenyl - 9 - benzylidene- 1 : 4-dim ethyl- 9 : 10-dihydroanthracene, m . p. 170°, is described.
9 : 10-Dipheriyl-l : 4-dimethylantliracene, m . p. 189°, is deriv ed from 10-phenyl-l : 4 -d im eth y lan th ro n e.
H . Wr e n. F lu o r a n t h e n e . O. Kr u b e r (Ber., 1931, 6 4 , [A ], 84—85).— T re a tm e n t of a n e u tra l ta r-o il fractio n , b. p. 370—390°, w ith sodium in solvent n a p h th a a t 160° yields a solid sodium d eriv ativ e from w hich te tra h y d ro flu o ran th e n e , ni. p . 75°, is o b tain ed a fte r decom position w ith w a t e r ; th e filtra te from th e sodium com pound re a d ily affords p yrene. O xidation of te tra h y d ro flu o ra n th e n e w ith sodium d ich ro m ate in glacial acetic acid gives (?) fluorenone-8-propionic acid, m . p. 137—13S°. T e trah y d ro flu o ran th en e u n ites w ith sodium an d th e m ix tu re of com pounds is tr a n s form ed b y carb o n dioxide in to carboxylic acids, from w hich a n acid, C17H140 2, m . p. 188° a fte r softening, is o b ta in e d ; w hen h e a te d above its m. p. o r distilled
■with lim e, i t affords te tra h y d ro flu o ran th e n e . I t is u nlikely t h a t th e ta r-o il fractio n co n tain s te tra h y d ro -
flu oranthene. H . Wr e n.
M e th o d of r e d u c i n g a r o m a t i c n i t r o - c o m - p o u n d s . T . E . d e Kie w ie t a n d H . St e p h e n (J.C .S., 1931, 82— 84).— C rystalline sta n n o u s chloride (SnCI2,2H20 ) is h e a te d w ith excess of acetic an h y d rid e u n til com pletely d e h y d ra te d ; th e resu ltin g so lution reduces nitro-com pounds to acetam ido- or, o ften w here possible (exceptions are m -chloronitrobenzene, th e n itrobenzoic acids, a n d o-nitrophenol), to p - chloroacetam ido-com pounds. p-C hloronitrobenzene gives p-ch lo ro acetan ilid e in absence of free hydrogen chloride, an d 2 : 4-diehloroacetanilide in its p re se n c e ; o-, m -, a n d p-nitro b en zo ic acids give th e corresponding am inobenzoic ac id s; p -n itro p h e n o l an d its chloro- d e riv a tiv e s give acetam id o p h en y l a c e ta tes, b u t o- n itro p h en o l a n d sim ilar d e riv ativ es give acetam ido- phenols, a p p a re n tly b y hyd ro ly sis of in te rm e d ia te ly form ed 1-m ethylbenzoxazoles. 3-Chloro-4-nitro- phenol, m . p. 120°, o b ta in e d b y n itra tio n of wt-cldoro- ph en o l (cf. U hlem ann, B er., 1869, 2, 1161; Chem.
E a b r. G riesheim -E lektron, G .P . 143,449), gives 3-chloro-4-acetamidophenyl acetate, m . p . 127°.
H . A. Piggott. H y d r o g e n a tio n of a n ilin e u n d e r p r e s s u r e in t h e p r e s e n c e of c e r i u m a n d l a n t h a n u m a s p r o m o t e r s . V. S. Sa d ik o v a n d A. J . Schagalov (J.
R uss. P h y s. Chem. Soc., 1930, 6 2 , 1635— 1642).—
T he influence of sm all q u a n titie s (1% ) of cerium a n d la n th a n u m oxides as p ro m o ters to th e m a in c a ta ly sts (osm ium a n d nickel) in th e h y d ro g en atio n of aniline u n d e r pressure w as in v estig ated . W ith osm ium , th e ad d itio n of cerium oxide does n o t affect th e tim e of h y d ro g en atio n , alth o u g h th e consum ption of hydrogen
is decreased. T he yield of benzene a n d cydohexyl- am ine is m u ch g re a te r, w hilst th a t of dicycZoliexyl- am ine is m u c h less, a n d m ore aniline is left unreduced, .so t h a t cerium oxide ap p ea rs to a c t as a n in h ib ito r on osm ium . W ith nickel in ste a d of osm ium , th e presence of cerium oxide som ew hat im proyes th e final yield, b u t th e m ain fa c to r in th e efficiency of th e c a ta ly s t ap p ears to be th e pre lim in ary h e a t tre a tm e n t of th e la tte r, w hich is ren d ered m ore sensitive to it b y a d d itio n of cerium oxide. I f la n th a n u m oxide is used, th is sensitiveness is still fu rth e r increased, w hilst th e te n d e n c y to p ro m o te th e co ndensation of th e re d u c tio n p ro d u cts is dim inished, th e cycZohexylamine c o n te n t in th o final m ix tu re increasing from 3 3 % in th e case of cerium oxide to 71-2% in th e case of la n th a n u m oxide, a n d t h a t of dic;/cZohexylaminc falling from 5 2 % to 33% . M. Zv e g in t z o v.
A c tio n of a lc o h o ls a n d e s t e r s o n a n ilin e h y d r o c h lo r id e . S. A. Bu s s e an d A. I . Tr a v i n (J. Ru s s. P h y s. Chcm. Soc., 1930, 6 2 , 1685— 1090).— A niline hy d rochloride a n d benzyl alcohol w hen h e a te d t o g e th e r gav e a 59% yield of phenylbenzylam ine, m . p.
35-5°. U sing benzyl a c e ta te , th e y ield w as m ore th a n 79% . O x idation w ith ferric chloride or su lp h a te gav e b e n z a ld e h y d e ; o x id a tio n w ith n itro so d im eth y lan ilin e gave b enzaldehyde to g o th er w ith som e azo xydim ethyl- aniline, m . p . 241°. W ith « -o c ty l alcohol aniline gives phenyloctylamine, b. p . 158— 158-5°/4 m m ., d 0-90S9,
nf, 1-5132, w hich yielded o ctald eh y d e on o x id atio n .
” M. Zv e g in t z o v. D e r iv a tiv e s of l - c h l o r o - 2 - n i t r o n a p h t h a l e n e . A. P . J . Ho o g e v e e n (Rec. tra v . chim ., 1931, 5 0 , 37—
40).— 2 -A cetn ap h th alid e is co n v erte d , th ro u g h th e cliloroam ine, b y a n excess of bleaching pow der solution in d ilu te acetic acid in alcohol a t 16° in to l-ch lo ro -2-a c e tn a p h th a lid e , w hich affords l-ch lo ro -2- n itro n a p h th a le n o (H odgson a n d Ivilner, A ., 1926, 279) a fte r hydrolysis, diazo tisa tio n , a n d tre a tm e n t of th e diazo-solution w ith potassiu m n itrite in th e p re se n c e of cu p ro u s-cu p ric su lp h ite. I t is co n v erted b y h e a t
ing w ith a n alcoholic solution of th e a p p ro p ria te am ine in a scaled tu b e a t ISO0 in to 1-am ino-, 1- methylamino-, m . p. 114°, a n d 1-cthylamino-, m . p.
77°, -2-nitronaphthalene, a n d b y alcoholic sodium disulpliide in to 2 : 2'-di nitrod i napli thy I disulphide,
m . p . 204°. J . W . Ba k e r.
M e c h a n i s m o f c h e m ic a l r e a c tio n s . I I . M e c h a n is m of th e s y n t h e s i s of s e c o n d a r y a n d t e r t i a r y a m i n e s b y r e d u c tio n . K . K i n d e e r [w ith W . De h n a n d W . Pe s c h k e] (A nnalen, 1931, 4 8 5 , 113— 126).— R ed u c tio n of benzylam ine o r p-plienyl- eth y lam in e w ith p allad iu m -b lack a n d hyd ro g en in boiiing alcohol gives, respectively, q u a n tita tiv e an d 10% yields of th e seco n d ary bases dibenzylam ine a n d di-((3-phcnylethyl)am ine, th e velocity of re d u c tio n of benzylam ine also being th e g re a te r in glacial acetic acid o r xylene. S im ilar re d u c tio n of (3-phenylethyl- am ine in th e presence of benzyl alcohol in xylene affords m ain ly (90% ) Ar-benzyI-(3-phenylethylam ine (also o b ta in e d b y c a ta ly tic re d u c tio n of benzylidene-P- p h en y leth y lam in e) a n d on ly 6% of d i-([3-phenylethyl)- am ine, d eterm in ed b y th e a m o u n t of a m m onia evolved.
R e d u ctio n of tliiobenzam ide w ith alum inium am algam a n d m o ist e th e r affords 85% of benzylam ine a n d 8%
of dibenzylam ine, a n d proceeds m ore ra p id ly th a n th e sim ilar re d u c tio n of p h en y lth io a cetam id e, w hich affords 26% a n d 66% of th e p rim a ry a n d seco n d ary bases, respectively. R ed u ctio n of th e m ix tu re of a-amino-(3- p h e n y le th y l alcohol a n d p h en y laeetald im in e (o b tain ed b y th e ac tio n of am m o n ia on phen y lacetald eh y d e) w ith alum inium am algam a n d w a te r affords di-(P- pheny leth y l)am in e, in ad d itio n to th e p rim a ry base, sim ilar re d u c tio n of a -d im ethylam ino-p-phenylethyl alcohol yielding p -p h en y leth y ld im eth y lam in e (D ecker an d B ecker, A ., 1912, i, 844). R ed u c tio n of phenyl- aceto n itrile in acetic acid a n d am m onium a c e ta te w ith hyd ro g en a n d p allad iu m -b lack a t 65°/2-5 a tm . gives, in a d d itio n to (3-phenylethylam ine a n d th e corresponding seco n d ary base, p-phenylethylidene-P - ph en y leth y lam in e, red u ced to di-(p-phenylethyl)- am ine in 60% yield. T he p ro p o rtio n of p rim a ry a n d secondary liases form ed d epends on th e acid p re se n t d u rin g th e re d u c tio n an d in aqueous-alcoholic eth y l a c e ta te, glacial acetic acid, a n d acetic acid containing hyd ro g en chloride, w ith h ydrogen a n d pallad iu m -b lack a t 35°/2-5 a tm ., th e p ro p o rtio n of these p ro d u c ts is 25, 50, a n d 90% a n d 70, 40, a n d 1% , respectively. Tho m uch g re a te r velocity of re d u c tio n of benzonitrile com pared w ith t h a t of p h en y laceto - nitrile re su lts in th e alm o st exclusive fo rm a tio n o f th e p rim a ry base in th e first case, w h ilst in th e la tte r a largo a m o u n t of th e seco n d ary am ine is also form ed.
S im ilar re d u c tio n of p h en y laceto n itrile in th e presence of d ip ro p y lam in e affords P -phenylethyldipropylam ine in a d d itio n to th e n o rm al p ro d u c t di-(p-phenylethyl)- am ine. T hese re su lts confirm th e follow ing m ech an ism fo r th e fo rm a tio n of seco n d ary bases :
CH2R - 0 H Z l> C H R :0 ii^ C H R :N H (I) o r C H2R -N H2
2 H / t \ C nV R-N H .,
tfl) C H2R - N :C H R ^ N H (C H2R )2; and R C N .!£ (I)£ £ C H R (O H )-N H2 ( I I ) - » R - C H : 0 + N H3 ; (I) or (II):
568— 572).
L C H ,R -N H , (cf. K in d le r, A ., 1923, i, J . W . Ba k e r. C o n v e rs io n of a ld e h y d e s i n t o h i g h e r m o le c u la r a m in e s . A. S k i t a , G. P e e i l , an d [in p a rt] H . W i n k e l e r (A nnalen, 1930, 4 8 5 , 152— 173).— The am ine, b. p. 110— 112°/15 m m ., o b ta in ed b y c a taly tic red u ctio n of «-propylidenecycZohexylamine (S k ita and W ulff, A ., 1927, 559) w ith colloidal p la tin u m in alcoholic acetic acid is cyclohexyl-(fi-methyl-n-amyl)- amine (I II) (hydrochloride, m . p . 139°; ■phenylurethane, m . p . 99°), id en tical w ith a specim en o b tain ed by sim ilar re d u ctio n of fi-methyl-&s-pentenylidenecyc\o- hexylamine (II), b. p. 118— 119-5715 m m ., obtained b y condensation of a-m ethyl-A °-pentenalclehydc (I) w ith cycZohexylamine. I n th e original red u ctio n com plete hydrolysis first occurs to give propalde- hyde w hich "by a n aldol condensation followed b y loss of w a te r affords th e p en ten ald e h y d e I . T his con
denses w ith cycZohexylamine to th e Schiff’s base II, w hich is less read ily h ydrolvsed a n d is red u ced to I I I : 2CH„Me-CH:N-C6H11— y C6H n -K H2-fC H2Mc-CHO
“ — yCHoMe-CHX'Me-CHO ( I ) W |
CH,Me-CH:CMe-CH:N*CGH1 j (II)— ->
C H 3 Ie-C H2-CILAIe-GH2-NH-CGH 1( ( I I I ) .
S im ilar re su lts are o b tain e d w ith Schiff’s bases derived from o th e r alip h atic (b u t n o t arom atic) aldehydes and
O R G A N IC C H E M IS T R Y . 3 4 3
cycZohexylamine, alth o u g h th e above case is th e only one in w hich hydrolysis is com plete. T he s tru c tu re of th e re d u c tio n p ro d u c ts is p ro v ed b y th e ir id e n tity w ith th e red u ctio n p ro d u c ts of th e in term ed ia te SchiS’s bases synthesised from cyc/ohexylam ine an d th e a p p ro p ria te u n s a tu ra te d aldehyde. T h u s ethyl- idenecycZohcxylamine is reduced to cycZohexylethyl- am ino (S%) (picrate, m . p. 231°) a n d cyclohexyl-n- bu ty lam in e (39% ) (also from A^-butenylideneoyelo- . hexylamine, b. p . 90— 91°/15 m m .) ; ?i-butylidene-, isovalerylidene-, n -heptylidene-, a n d y-phenylpropyl- idene-cycfohexylamine, by sim ilar red u ctio n , aS ord, respectively, cyclohexyl-((i-ethyl-ii-hexyl)amine (78% ), b. p. 140— 148°/15 m m . {hydrochloride, m . p. 95°;
picrolonate, m . p . 225— 226° (decom p.)] (also from fi-cthyl-A$-hexylidenecyclohexylamine, b. p . 139— 143°/
13 m m .) ; eyc\ohexyl-(z-melhyl-^-isopropyl-n-hexyl)- amine (15% ), b. p . 143— 145°/11 m m . (hydrogen oxalate, m. p. 193-5— 194-5°; hydrochloride, m . p.
105°) (also from z-methyl-fi-isopropyl-AP-n-hexylidene- cyclohexylamine, b. p. 146— 152°/16 m m .); cyclohexyl- (p-amyl-n-nonyl)amine (42-3%), b. p . 208— 210°/
17 m m . (hydrochloride, m . p. 9 0 °; hydrogen oxalate, m, p. 153°) (also from {-am yl-As-n-?ionenyli denecyclo- hexylamine, b. p. 208— 211°/11 m m .) ; cyclohexyl- (z-phenyl-?j-benzyl-n-amyl)amine (hydrochloride, m . p.
169— 170°; hydrogen oxalate, m . p . 172°) (also from z-phenyl - ¡3 - benzyl - A^-i\-pentenylidenecyc\ohexylamine, b.
p.
265— 270°/16 m m .), to g eth er w ith th e n o rm al reduction p ro d u cts, of w hich cyclohexyl-n-heptylamine, b. p. 132— 135°/16 m m . (hydrochloride, m . p. 211—212°), is new . F ro m isovalerylidene-ethylam ine is obtained N - (z - methyl - ¡3 - isopro p yl - n - hexyl)ethyl-amine, b. p. 213—220° [picrolonate, m . p. 22 1—222° (decomp.)]. W h en th e re d u ctio n of th e Scliiff’s base is effected in th e presence of a n o th e r ald eh y d e th is may also u ndergo a n aldol condensation w ith th e a ld e hyde form ed b y hydrolysis of th e Sehiff’s base a n d m ixtures of several am ines are th e n form ed b y th e mechanism given above. T h u s red u ctio n of propyl- idenecycfohexylamine in th e presence of acetald eh y d e affords, in a d d itio n to th e p ro d u c ts o b tain ed above, eyc\ohexyl-({-methylbutyl)aminc (29-5%), b. p . 97— 99°/
15 mm. (hydrochloride, m . p . 234°; phenylurethane, m- p. 118°) (also from {-methyl-AP-bulenylidenecyclo- hexylamine, b. p. 100— 105°/15 m m .), w h ilst w ith benzaldehyde as th e second com ponent a re o b tain ed eyc\ohexyl-(y-phenyl-{-mcthylpropyl)annine (1 1% ), b. p.
164—168°/15 m m . (hydrochloride, m . p. 184°; phenyl- urethane, m . p. 116°) (also from y-phcnyl-{-mcthyl-A^- propenylidenecyclohexylaminc, b. p . 168— 176°/14 mm.), an d cyciohexylbenzylam ine. R ed u c tio n in th e presence of fu rfu rald eh y d e affords cyc\ohexyl-(y-furyl- {■methylpropenyl)amine (8% ), b. p. 166— 172°/12 m m . (hydrochloride, m . p. 180°) (also from y-furyl- {-methyl-AP-propenylidmecyclohexylaniine, b.
p.
15S—162°/12 m m .), to g e th e r w ith its dihydro- (0-7% ), b. p.
loo— 160°/12 m m ., a n d tetrahydro- (8% ), b. p. 144r—
149°/12 m m . (hydrogen oxalate, m . p. 165°) -derivatives (the position of th e double linking in all th re e p ro d u c ts is u n d eterm in ed ),an d cyclohexylfurylamine, b. p. 123—
124° (phenylurethane, m . p. 113°) (also from J'urJuryl- idenecyclohexylamine, b. p. 131-5— 135-5°/lS m m .).
R eduction of wobutylidcnecycZohexylamine in th e presence of form aldehyde affords
cyclohexyl-(y-hydroxy-(3{-dimethylpropyl)aminc, b. p . 123— 125°/12 m m ., m . p. 38° (hydrochloride, m . p. 224°; phenylur ethane, m . p. 150°) (also from y-hydroxy-{{-dim cthylpropyl- idenecyclohexylamine, b. p. 10S—110 °/12 m m .).
J . W . Ba k e r. [ P o s s ib le y e llo w c o n te n t of t h e a c id ic , r e d s o lu tio n s of m e th y l- y e llo w .] A. Ha n t z s c h a n d A. Bu r a w o y (Ber., 1930, 6 3 , [£ ], 3172— 3176; cf.
A ., 1930, 1280).— In reply to T hiel (A., 1930, 1573), reasons are ad v an ced in fa v o u r of th e view t h a t in s a lt solutions of p-am inoazobenzenes in 2A -hydrochloric acid, w hich in agreem en t w ith Thiel co n tain p ra c tic a lly
A ., 1930, 1280).— In reply to T hiel (A., 1930, 1573), reasons are ad v an ced in fa v o u r of th e view t h a t in s a lt solutions of p-am inoazobenzenes in 2A -hydrochloric acid, w hich in agreem en t w ith Thiel co n tain p ra c tic a lly