atives.
R . W . J a c k s o n an d R . I I . M a n s k e(J.
Amor. Chcra. Soc. 1930,
52,
5029— 5035).—Ethyl
cyc/ohexanonc-2-carb o x y late an d benzenediazonium chloride re a c t in presence of ice a n d alkali hydroxide, form ing th e p h en ylhydrazone, m . p. 142— 143° (all m . p. are corr.), of e th y l hydrogen a-ketopim elatc.T re a tm e n t of th is w ith alcoholic sulphuric acid gives ethyl y-2-carbcthoxy-3-indolylbutyrate, b. p. 235°/7 m m ., m. p. 76° (corresponding dimethyl ester, m . p. 64°); a sm all a m o u n t of s-diphenylcarbam ide is isolated d u rin g th e d istillatio n of th ese esters. T he corre
sponding dicarboxylic acid, m . p. 193— 194° (decom p.), is decom posed b y h e a t to a m ix tu re of 1-keto- 1 : 2 : 3 : 4 -tetrah y d ro carb azo le (sm all am o u n t) and y - 3 -indolylbutyric acid, m . p. 124°, w hen purified th ro u g h its methyl ester, m . p. 73— 74°. y-3-Indolyl- butyrhydrazide, m. p. 1 1 2°, is co n v erted b y th e usual m eth o d in to th e azide an d thence, b y tre a tm e n t w ith w a te r or m e th y l alcohol, in to s-di-(y-3-indolylpropyl)- carbamide, m .
p.
124°, o r methyl y-3-indolylpropylcarb- amate, respectively. B o th these com pounds re a c t w ith p h th a lic an h y d rid e a t 230°, form ing y-3-indolyl- propylphlhalim idc, m . p. 132°, hydrolysed b y aqueous- alcoholic h y d razin e to y-3-indolylpropylam ine.R ed u ctio n of m e th y l (3-3-indoIylpropionate w ith sodium a n d alcohol gives y-3-indolylpropyl alcohol, solidifies a t 0° (picrate, m .
p.
10 1°; phenylcarbimide d e riv a tiv e, m . p. 94°). 8-3-Indolylbutyl alcohol, m .p.
32— 33° (picrate, m .
p.
192°; phenylcarbimide d e riv a tiv e, m . p. 88°), is p rep ared sim ilarly from m eth y l y -3 -in d o ly lb u ty rate. W hen y-3-indolylbutyrazide is first decom posed in w arm benzene an d th e r e s u lta n t p ro d u c t tre a te d w ith h ydrogen chloride, a b o u t 5 % of 2-keto-2 : 3 : 4 : 5-tetrahydrohomo-3-carboline, m . p.220°, is p ro d u ced (cf. A., 1927, 256). 8-3-Indolyl- butylmalonic acid, m . p. 177°, is produced to g e th er w ith m u ch te tra h y d ro carb azo le from e th y l sodio- m alo n ate a n d 8-3-iudolylbutyl p -to lu en esu lp h o n ate (cf. Peacock a n d T h a, A., 1928, 1115).
T he fo rm atio n of th e above carbazole d eriv ativ es em phasises th e r e a c tiv ity of th e 2-hydrogen ato m in
indole. H . Bu r t o n.
Synthesis of hydroxy-AT-m ethylnaphthindole- quinone and W -methylnaphthisatinquinone. Z.
K i t a s a t o a n d C. S o n e (Bull. Chem. Soc. J a p a n , 1930,
5,
348— 354).— E th y l 3-brom o-l : 4 -n ap h th aq u in o n y l-3-m alonate (L ieberm ann, A., 1899, i, 373, 522) and alcoholic m eth y lam in e give a m ix tu re of 3-bromo- 1 : 4-naphlhaquinonyl-2-acetmcthylamide, m . p. 165°, an d ethyl 2-keto-\-methyl-2 : 3-dihydronaphthindole- 4 : 9-quinone-3-carboxylate (I), yellow, decom p, a b o u t 220° a fte r tu rn in g bluish-violet a t 190°. W hen I is boiled w ith alk ali in air, 2-hydroxy-1-methylnaphth- indole-4 : 9-quinone, deep blue, n o t m elted a t 300°, is produced. T his is oxidised b y n itric a n d sulphuric acids to l-methylnaphthisatin-4 : 9-quinone, m .p.
268°.V arious reactio n s of in d ig o tin , n a n d a z u rin (cf. A .(
1927, 1094), a n d th e ab o v e h y droxyindole are com pared.
^H-CChEt
NMe
( I .)Ethyl G-bromo-3 : 4-dimethoxycinnamate, m . p . 114—
115° (the frco acid, m . p . 244°, is p re p a re d b y th e u su al m eth o d from 6-b rom overatraldehyde), a n d ethyl 3-bromo-l : 4-naphtliaquinone-2-carboxylate, m . p.
119°, p rep ared from 2 : 3 -d ib ro m o -l : 4 -n a p h th a - quinone an d e th y l fo rm ate in presence of alcoholic sodium ethoxide, are converted b y alcoholic m eth y l- am ine in to G-bromo-3 : i-divielhoxycinnam-mcthyl- amide, m . p. 1S3°, an d 3-bromo-l : 4-naphtha quinone-2 -carboxylamide, m . p. 164— 165°, respectively.
H . Bu r t o n.
O rgano-alkali com pounds. VIII. Reactions between lithium alkyls, pyridine, and condensed pyridine system s.
K . Zi e g l e r a n d II . Ze i s e r(A nnalen, 1930. 4 8 5 , 174— 192).— T he p re p a ra tio n of p y rid in e d eriv ativ es b y th e p rim a ry a d d itio n of lith iu m alk y ls an d ary ls (A., 1930, 1191) h as been e x ten d ed to various s u b s titu te d p yridines an d con
densed p y rid in e system s such as quinoline, iso- quinoline, a n d acridine. D ecom position of th e a d d itiv e p ro d u c t of quinoline a n d lith iu m b u ty l (in benzene solution) w ith w ate r affords a 90% yield of 2-butyl-l : 2-dihydroquinoline, b. p. 160— 1 6 2°/14m m ., 128°/0-06 m m ., iff® 0-9961, 71“ '* 1-56959, co n v erted b y h ea tin g in nitrobenzene in to 2-butylquinoline, b. p . 153°/14 m m ., <?fl* 1-0018, ri-™ 1-56932 (picrate, m . p.
162— 163°). T h e la tte r is also o b tain ed (50— 60%
yield) b y th e rm a l decom position of th e A -lith iu m 2- b u ty ld ih y d ro q u in o lin e in a n atm o sp h ere of nitrogen, a n d in th is case fractio n al cry sta llisatio n of th e p ic ra te affords a sm all q u a n tity of a n isom eric picrate, m . p. 145°, in d icatin g th a t a sm all am o u n t of 1 : 4- a d d itio n of th e lith iu m b u ty l occurs. T herm al decom position of th e crystalline a d d itiv e com pound of lith iu m phen y l an d quinoline causes decom position of th e expected p ro d u c t, b u t decom position w ith w a te r affords a m ix tu re of 2-phenylquinoline a n d its 1 : 2-di- h y d ro -d e riv ativ e, converted com pletely in to th e form er b y h e atin g in nitrobenzene. T h e lith iu m d eriv ativ es o b tain ed w ith tsoquinoline are m ore sta b le to h e a t ; t h a t from lith iu m b u ty l is decom posed b y w a te r in a n atm o sp h ere of nitro g en to 1-butyldihydro- isoquinoline, b. p. a b o u t 135°/0-4 m m ., w hich is a u t- oxidisable a n d is c o n v erted d irectly b y h e a tin g in n itro b en zen e in to l-butyUsoqmnoline, b. p. 154—
157°/14 m m . (picrate, m . p. 185-5°). D ecom position of th e p ro d u c t o b tain ed from laoquinoline a n d lith iu m ph en y l w ith w a te r causes a large a m o u n t of d e h y d ro g en atio n of th e dihydro-com pound, a n d h e a tin g w ith nitrobenzene gives 1-phenylisoquinoline, m . p. 97°
(lit. m . p. 87— 88°: th e specim en, m . p. 80°, o b tain ed b y B orgm ann a n d others, A., 1930, 1596, is im pure).
9-B utyl-9 : 10-dihydroacridine, obtain ed sim ilarly, has m . p. 105° (lit. m . p. 98— 100?). D e h ydrogenation of alk yldihydroacridines to th e acridine d e riv a tiv e occurs sm oothly w hen th e y are h e a te d w ith a slight
excess of m ercuric oxide in boiling alcohol. T h erm al decom position, in a sealed tu b e a t 100°, of th e p ro d u c t o b tain ed b y th e actio n of lith iu m b u ty l in benzene on 2 -b u ty lp y rid in e affords, m ain ly , 2 : 5(?)- dibulylpyridine, b. p. 243— 244° [chloroplatinate, m . p.
192-5— 193° (decom p.)]. T he re a c tio n betw een lith iu m alkyls a n d 2-su b stitu te d p y rid in e or quinoline d eriv ativ es yields lith iu m d eriv ativ es of th ese su b stances, th e s tru c tu re of w hich m a y be e ith e r ty p e I o r I I . W ith alk y l halides th e y behave as if th e y
(I-)
!H2L i I
A
J:CH2 (II.) K L ipossessed s tru c tu re I . T h u s th e lith iu m com pound o b tain ed from lith iu m p h en y l an d q uinaldine reacts w ith pro p y l brom ide, benzyl chloride, an d allyl chloride to give, respectively, 2-butylquinoline, 2-(l- p h enylethylquinoline, m . p . 28° (lit. m . p . a b o u t 30°), a n d 2-Av-butenylquinoline, b. p. 152-5— 154°/14 m m ., d]7 J 1-0255, n'J4 1-58647 (picrate, m . p. 143°), w h ilst w ith benzophenone is o b tain ed aa-diphcnyl-$-(2-quinolyl)- ethyl alcohol, C9H6N-CH2-CPh2-OH, m . p . 165°, d e h y d ra te d b y co n c e n tra ted sulphuric a n d acetic acids to 2-(Pj-phenylslyryl)quinoline, m . p. 103— 103-5°.
Sim ilarly, lith iu m m eth y l co n v erts a-picolinc, w ith evolution of m eth an e, in to its lithium d eriv ativ e, w hich reacts w ith benzyl chloride to give 2-(p-phenyl- ethyl)quinoline (picrate, m . p. 127°). On th e o th e r h an d , w ith carbon dioxide th ese lith iu m d eriv ativ es re a c t according to th e s tru c tu re I I , th e p ro d u cts being th e p a re n t bases, p resu m ab ly deriv ed from a n in te rm e d ia te A -carboxylic acid. D ecom position of th e reactio n p ro d u c t of 9-m ethylacridine a n d lith iu m p h en y l w ith w a te r affords only th e original base.
J . W . Ba k e r.
Synthesis of quinoline com pounds. VI. P re
paration of acylam ido-derivatives of 8-hydroxy- quinoline.
K . M a ts U m u ra an d C. So n e (J. Am er.Chern. Soc., 1931, 5 3 , 177— 179).— T he following acetam idohydroxyquinolines are o b tain ed w hen th e ap p ro p ria te am inohydroxyquinolines (1 m ol.) are tre a te d w ith acetic a n h y d rid e (1-1 m ols.) in presence of e th e r a n d sodium a c e ta te a t th e o rd in a ry te m p e r
a tu re fo r 3 d ay s : 7 - iodo-5-a cetamido - 3-hydroxy-, m . p.
212° [hydrochloride, m . p . 196° (decom p.)]; 5-acet- amido-S-hydroxy-, m . p. 218— 219° [hydrogen sulphate, m . p . 263° (d eco m p .)]; 5-acetamido-G-hydroxy-, m . p.
278° (decom p.) (hydrogen sulphate); 7-acetamido-S- hydroxy-5-tnethyl-, m . p. 203— 204° (sulphate, m . p.
1S0°). l-Amino-S-hydroxy-S-methylquinoline, m . p.
141— 142° [picrate, decom p. 215— 220°; ON-dt- acetyl d eriv a tiv e, m . p. 222° (hydrogen sulpluite, m . p.
183°); ON-dibenzoyl d eriv ativ e, m . p . 181°, p repared b y a m eth o d sim ilar to th e above using benzoyl chloride in place of acetic an h y d rid e], is o b tain ed w hen 7-nitroso-8-hydroxy-5-m ethylquinoline is reduced w ith stan n o u s chloride an d hydrochloric a n d acetic acids. 5-Benzamido-S-hydroxyquinoline, m . p . 237—
23S° [hydrogen sulphate, m . p. 225— 227° (decom p.)], is p rep ared b y th e p y rid in e m eth o d in th e cold. M ethyl- a tio n of 8-hydroxy-5-m ethylquinoline w ith m ethyl iodide a n d m ethyl-alcoholic p o tassiu m hydroxide gives S-methoxy-5-methylquinoline,
b.
p . 298— 302°/773O R G A N IC C H E M IS T R Y . 3 6 5
nun. [-picrate, in. p. 180— 181°; cJdoroplatinatc, m . p.
224° (decom p.)]. H . Bu r t o n.
1 - u - H a lo g e n o a lk y lts o c fu in o lin e s a n d t h e i r d e r iv a tiv e s . R . C iitld a n d F . L. P y m a n (J.C .S., 1931, 36— 49).— 8-Chloroualero-$-veralrylelhylamide, in. p. 60— 62° (corr.), w as co n v erted b y phosphorus oxychloride in to 6 : 7-dimethoxy-l-S-chlorobutyl-3 : 4- dihydroisoquinolinc (I) [hydrochloride, m. p. 172— 173°
(corr.)], isolated as its picrate, m . p. 156— 157° (corr.).
The sam e su b sta n ce w as'also o b tain ed to g e th e r w ith a little of th e p ic ra te of I I from S-bromovalero-fi-veratryl- ethylamide, m . p. 70—72° (corr.). C yclisation of I to 5 : bi-dehydro-10 : ll-dim ethoxy-1 : 2 : 3 : 4 : 6 : 7-liexa- hydrobenzpyridocolinium chloride,
(M et J ' --vl (H ), m . p . 197— 198° (corr.) U;Ue\ / x[CH2]2-N Cl
(air-dried salt, -|-HC1,2H20 , effervesces a t 103° a fte r softening a t 90°), iso lated as th e picrate, m . p. 185—
186° (corr.), w as effected b y w arm ing. T he iodide has m. p. 210—212°. R e d u ctio n of I I gave 1 0 : 11-di- methoxy - 1 : 2 : 3 14 : 6 : 7 - hcxahydrobenzpyridocoline, m. p. 54°, b. p. 225°/15 m m . [hydrochloride, m. p.
235—237° (corr., d e c o m p .); p ic ra te , m . p. 172— 174°
(corr.); a -metliiodide, m . p. 228° (c o rr.); ^-metliiodide, m. p. 244— 245° (corr.). P a rtia l conversion a—
at 250°]. y-Bromobulyro-fi-veratrylethylamidc, m . p.
05° (corr.), w hich read ily decom poses in to b u ty ro - lactone an d [i-varatrylethylamine hydrobromide, m . p.
179— 180° (corr.), w ith phosphorus oxychloride gave, after tre a tm e n t of th e p ro d u c t w ith picric acid, a m ixture of 6 : 7 -dim ethoxy-l-y-chloropropyl-3 : 4-di- hydroisoquinoline p ic ra te (crude), m . p. 163— 164°, and 4 : 13-dihydro-Q : 10-dimethoxy-I : 2 : 3 : 5 : 6 : 13- hexahydrobenzpyrrocolinium picrate, m. p. 201— 202°
(corr.). T he corresponding chloride (III), m . p . 120—
122° (corr.) ( + 2 H 20 ), m . p. of an h y d ro u s m a te rial 204—205°, on ^eduction w ith tin a n d hydrochloric acid in alcohol g av e 9 : 10-dimethoxy-l : 2 : 3 : 5 : 6 : 13- hexahydrobenzpyrrocoline, in. p. 88— 89° (corr.) [hydro
bromide, m. p. 186° (c o rr.); picrate, m . p. 187° (corr., decomp.)]. T he re lativ ely g re a te r te n d en cy to form the five-m cm bered rin g in I I I th a n th e six-m em bered ring in I I is em phasised. B y sim ilar reactions, chloro- aceto-$-veratrylethylamide, m . p. 96° (corr.), an d bromo- a<xto-$-veralrylelhylamide, m . p. 115° (corr.), w ith phosphorus oxychloride gave 6 : 7-dimethoxy-1-chlor o- methyl-3 : ‘i-diliydroisoquinoline hydrochloride, d ark en s at 210°, effervesces a t 217° [picrate, m . p. 196° (corr., decomp.)], which w ith aqueous p o tassiu m cyanide yielded \-cyano-G : 7-dimethoxy-l-chloromethyllelra- hydroisoquinoline, softens a t 122°, m . p. 125° (corr., decomp.). W ith aqueous-alcoholic p o tassiu m cyanide the la tte r yielded 6 : 7-dimethoxy-l-cyanomethyl-3 : 4- dihydroisoquinoline (IV ), m . p. 173° (corr.) [hydro
chloride, m. p. 205— 206° (c o rr.); picrate, m . p . 225°
(decomp.)], also o b tain ed from cyanoaccto-$-veratryl- clhylamide, m. p. 115° (corr.), 127— 128° a fte r resolidi
fication, a n d phosphorus oxy-chloride. R ed u c tio n of IV w ith sodium a n d alcohoi gave, a fte r tre a tm e n t of the crude base w ith picric acid, 6 : 7-dimethoxy-\-$- aminoctkyltetrahydroisoquinoline dipicrate (40% yield), m. p. 205° (c o rr.); i t crystallises from alcohol w ith L tO H [dihydrochloride + H 20 , m . p . 276— 277° w ith
effervescence (corr.)]. B rom oaeeto-(3-veratrylethyl- am ide w ith pho sp h o ru s p en to x id e in xylene led to 6 : 7-dimethoxy-l-bromomethyl-3 : ^-dihydroisoquinoline picrate, m . p . 190— 191° (decom p., corr.), chloroaceto- p-m-melhoxyplienylethylamide, m . p. 56— 57° (corr.), w ith phosphorus oxychloride gave 6-methoxy-l-chloro- methyl-3 : ‘i-dihydrolsoquinoline picrate, m . p. 169—
170° (uncorr.), a n d chloroaceto-$-piperonylethylamide, m . p. 72° (corr.), w ith th e sam e re a g e n t gave 6 :7 - methylenedioxy-1 -chloromethyl-3 : 4t-dihydroisoquinoline picrate, m . p. 179— 180° (corr., dccom p.), b u t w ith fi-chloropropiono-fi-veratrylethylamidc, m . p. 102—
103° (corr.), i t gave no isolablo p ro d u ct.
A n a tte m p t to p re p a re 6 : 7 -d im eth o x y -l-am in o - m ethyl-3 : 4-dihydrofsoquinoline from hippuro-$- veratrylethylaviide ( - f H 20 ), m . p . 85— 95°, b y d e h y d ra tio n w ith pho sp h o ru s oxychloride followed b y hydrolysis, led u n ex p ected ly to w h a t is considered to be 9 : \0-dimethoxy-3-plienyl-o : Q-dihydrobenzgly- oxalocoline (V), m . p . 1870 (corr.) [hydrochloride, m . p.
286— 287° (corr., d e c o m p .);
hydrobromide, m. p. 293°
(c o rr.); metliiodide, m . p. 255°
(c o rr.); picrate, m . p. 226—
227° (c o rr.); m onom tro-derivative, m. p. 202° (corr.)].
D em eth y latio n of V yielded 9 : 10 - dihydroxy-3 -phenyl- 5 : G-dihydrobenzylgoxalocoline hydrochloride (-J-3H20 ), m . p. 293° (corr.). Hippuro-$-phenylethylamide has m . p . 161° (corr.).
R o n e of a n u m b er of th ese sub stan ces possessed m a rk e d am cebicidal, a n tim alarial, o r try p an o cid al a c tiv ity . J . D . A. Jo h n s o n.
P rep a ra tio n of b rom in ated cin ch op h en s [2- p h en ylcin ch on in ic acid s]. H . G. L i n d w a l l , J . B a n d e s , a n d I. W e i n b e r g (J. A m er. Chem. Soc., 1931,
53,
317— 319).— Is a tin re a c ts w ith p -m e th o x y - a n d p-brom o-aeetophenones in aqueous-alcoholic p o tassiu m h y d ro x id e form ing 2-anisyl-, m . p. 216°, an d 2-p-bromophcnyl-cinclioninic acids, m. p. 293°, respectiv ely . Sim ilarly, 5 : 7-dibrom oisatin (conveniently p re p a re d b y b ro m in atin g isa tin in 95% alcohol) re a c ts w ith acetophenone a n d p -m e th o x y ace to - phenone to give 6 : S-dibromo-2-phenyl-, m . p . 270—
271°, an d 6 : 8-dibromo-2-anisyl-cinchoninic acids, m . p. 263— 264°, respectively. H . Bu r t o n.
D erivatives of pyrrole. I. Synthesis of 3- keto-4 : 5-dihydrodi-(l : 2)-pyrrole and 8-keto- 5 : 6 : 7 : 8-tetrahydropyrrocoline.
G. R . Cle m oa n d G. R . Ra m a g e(J.C .S., 1931,49— 55).— P o tassiu m p y rro le a n d e th y l c h lo ro acetate in benzene gave ethyl
l-pyrrylacetate, b. p . 112°/20 m m ., h y drolysed to 1 -pyrrylacetic acid, m . p. 91° (amide, m . p . 169°).
E thyl (3-1 -pyrryVpropionate, b. p . 122°¡23 m m ., an d
¡3-1 -pyrrylpropionic acid, m . p. 62° (amide, m . p. 81°), w ere p re p a red sim ilarly. C yclisation of succino-n- butylimidc, b. p. 140°/17 m m . (from p o tassiu m succinim ide a n d w -butyl b ro m id e; 80% yield), to a d e riv a tiv e of 5 : 6 : 7 : 8 -tetrah y d ro p y rro co lin e could n o t be effected. P o tassiu m p yrrole w ith (3-chloroethyl,
¡3-cyanoethyl, a n d y-chloropropyl toluene-p-sulphon- a te s yielded 1 -$-chloroethylpyrrole, b. p. 84°/20 m m ., 1 -p-cyanoethylpyrrole, b. p. 140°/20 m m ., an d 1 -y-chloropropylpyrrole, b. p. S7°/15 m m ., respectively.
OM(
OMe1
c:c h -N -C P h [CEL,], (V.)
C yclisation of l-fJ-cyanoethylpyrrole to 3-£eto-4 : 5-di- hydrodi-(l : 2)-pyrrole, m . p. 54° (piperonylidene d e riv a tiv e , m . p. 194°), w as effected b y tre a tm e n t w ith h ydrogen chloride in d ry e th e r in presence of zinc chloride, th e p ro d u c t being isolated as its sem i
carbazone, m . p. 211°. y-B ro m o b u ty ro n itrile a n d p o ta ssiu m p y rro le gav e y-l-pyrrylbulyronitrile, b. p.
152°/23 m m ., cyclised to 8-keto-o : 6 : 7 : 8-tetrahydro- pyrrocoline, m. p. 34° (semicarbazone, m . p. 193°;
piperonylidene d e riv ativ e, m . p. 136°). Ethyl (3-1- pyrroylpropionate, m . p . 50°, b. p . 162°/22 m m ., and (3-1-pyrroylethyl methyl ketone, b. p . 14S°/16 m m . {phenylhydrazone, m . p. 131°; semicarbazone, m . p.
190°), are also described. J . D. A Jo h n s o n.
Action of nitric acid on polycyclic indole derivatives. IX.
S. A. Br y a n t a n d S. G. P . Pl a n t (J.C .S., 1931, 93— 105).--7 : 8-D ih ydro-^ - naphtha pent indole (I), m . p. 167° [p icrate, m . p.167° (decom p.)], p rep are d from cyc\opentanone-a- naphthylhydrazone, m. p. 95°, on tre a tm e n t w ith acetic an h y d rid e containing sulphuric acid gave tw o isom eric acetyl d e riv a tiv e s; one, th e 10-acetyl com p o u n d , m . p. 157°, rev erted to th e base on hydrolysis, th e o th er (m. p. 215°) is presum ed to be 1 (l)-acetyl- 7 : S-dihydro-*$-7iaphthapenlindole, since i t ca n n o t be hydrolysed, a n d i t form s a n oxime, m . p. 236°
(decom p.). cycloPentanone- (3 - naphtliylhydrazone, m . p. 77°, sim ilarly gave 9 : iQ-dihydro-a.' -naphtha- pentindole ( I I ) , m .p . 103° [p icrate, m .p . 189° (decomp.);
benzoyl d eriv ativ e, m . p . 196°; carbethoxy-dcvivativc, m . p. 160°]. T his p ro d u c t could also be a n isom eric su b stan ce th e fo rm atio n of w hich w ould involve fusion of th e indole a n d n a p h th alen e nuclei th ro u g h th e (3(3'-positions of th e la tte r. T his c o n stitu tio n is considered im probable, since th e analogous cyclisation of ci/cZohexanone-p-naphthylhydrazone lias been show n to lead to th e cc[3-derivative (O akeshott an d P la n t, A., 1928, 1023). A c ety latio n of I I w ith acety l chloride in acetone in presence of alkali gave 7-acetyl
's) : Id-dihydro-’x'-naphthapentindole, m . p . 170°
(readily hydrolysed to th e base), w hich w ith acetic an h y d rid e in presence of co n ce n trated sulphuric acid gave 5( 1): 7-diacctyl-G : \0 -d ih y d ro -a .'-naphthapenlin- dole (T I T ), m. p. 234°. H ydrolysis of th e la tte r gave 5( l)-acetyl-9 : 10-dihydro-a'fi'-naphthapentindole, m . p.
239°, w hich could be re a c e ty late d to I I I an d gave a benzoyl d eriv ativ e, m . p . 163°. N itra tio n of th e 1-acetyl, 1-benzoyl, a n d 1 -carbethoxy-derivatives of
I I gave 5(l)-nitro-7-acetyl-, m . p. 247°, 5-( l)-nitro-7 - benzoyl-, in. p. 259°, a n d 5( t)-nitro-l-carbelhoxy- m .p . 202°, -9 : lO-dihydro-tx.'p '-naphthapentindoles, each of w hich on hydrolysis yielded 5( l)-nitro-9 : 10- dihydro-a.'-naphthapentindole, m . p. 228°. F ro m th e c arb eth o x y -d eriv a tiv e a dinilro-com pound, m . p.
220° (decom p.), w as also obtained.
C yclisation of 2-metliylcyriohexanone-(3-naph-
t h y l l y d r a z o n e gav e tw o p ro d u cts, I V , m . p . 115° [picrate, m . p. 201° (decomp.)], a n d V, m. p.
92° (picrate, m . p. 166°), th e form er of w hich wras show n to be S-methyl-S : 9 : 10 : ll-tctrahydro-a'fi'- naphthacarbazole, since d e hydrogenation led to 8-melhyl-a.'$'-naphthacarbazole, m . p. 144°, ra tio n ally sy n th esised from 2-hydroxy-3-naphthoic acid a n d o-tolylhydrazine th ro u g h 8-m
ethyl-a'|3'-naphthacarb-azole-6-carboxylic acid, m . p. 320°, b y d ecarboxyl
a tio n of th e la tte r. B y analogy, to p ro d u c t V th e c o n stitu tio n of \2-methyl-8 : 9 : 10 : 11 -tetrahydro- a'fi'-naphthacarbazolenine is assigned. T he con
stitu tio n s given to IV a n d V by C ecchetti a n d Ghigi (A., 1930, 787) are therefore incorrect.
T re a tm e n t of 5 : 6-dihydro-aj3-naphthacarbazole w ith acetic an h y d rid e containing a little sulphuric acid gave th e 1( 1)-dcelyl d eriv ativ e, m . p. 253°, b. p.
a b o u t 370°/40 m m ., n o t hydrolysed by alcoholic potassium hydroxide, a n d form ing a n oxime, m . p. 292°
(dccomp.).
B enzoylation of benzopentindole gave th e 7-benzoyl d eriv ativ e, m . p. 1S7°, w hich, tre a te d in acetic acid w ith n itric acid, gave ld-nitro-d-hydroxy-7- benzoyl-6 : Id-dihydrobenzopcntindolc, m . p. 169°
(decom p.), hydrolysed b y aqueous potassium hydroxide to 14-nitro-G-hydroxy-G : 14-dihydrobenzo- pentindole [not pu re, m. p . 200° (decom p.)].
J . D. A. Jo h n s o n.
Condensation of hydantoin w ith o-nitrohenz- aldehyde.
J . Iv o z a k a n d L . M u si A t (Bull. A cad.Polonaise, 1930,
A,
432— 438).— H y d a n to in and o-nitrobenzaldehyde condense in presence of zinc chloride a t 100— 110°, form ing 5-o-nitrobenzylidene- hydantoin, 111. p. 27S— 280° (decom p.), reduced b y red phosphorus a n d hydriodic acid to th e quinoline derivative (I), m . p. 348— 349°.N itra tio n of 5-o-nitrobenzylidene- h y d a n to in affords th e 1 -nitro- deriv ativ e, m . p. 224— 226° (de
com p.), w h ilst b ro m in atio n and ch lo rin atio n in acetic acid gives th e
\-bromo-, m. p. 247— 24S°, a n d th e 1 : 3-dichloro- d eriv ativ es, m . p. ISO— 182° (decom p.), respectively.
O x id atio n of th e n itro b en zy lid en eh y d an to in w ith ozone in acetic acid affords o-nitrobenzaldehyde and p ara b a n ic acid, w hilst o x id atio n of its 1-nitro- and halogeno-derivatives w ith alkaline p o ta ssiu m p e r
m an g a n a te gives o-nitrobenzoic acid. H . Bu r t o n.