amide, m; p. 95— 96°, w ith form ation of tliioacet- benzylamide, m . p. 62— 63°, is prepared sim ilarly.
H . E . F . N o t i o n . C o m p o sitio n a n d s t r u c t u r e of th e p o ly m e rid e of h y d ro c y a n ic a c id . E . G e is c h k e v its c h -T e o - oh im ovsk i (R ocz. Chem., 1928, 8, 165— 174).— The polym eride of hydrocyanic acid form ed from 4 m ols.
of th e latter gives on condensation w ith glyoxal 2 :Z-dicyanopyrazine, m. p. 132-5— 133°. I t hence follow s th a t th e tetram eride of hydrocyanic acid m ust be th e dinitrile of diam inom aleic acid; th is con
clusion is further supported b y th e form ation of 4 : 5-d icyan o-l : 2 : 3-triazole from th e tetram eride and nitrous acid. R . Teuszkow ski.
I n te r a c tio n of h y d ro g e n s u lp h id e w ith a m in o - a n d im in o - a c id n itr ile s . E . G a t e w o o d and T. 33.
J o h n s o n ( J . Amer. Chem. Soc., 1928, 5 0 , 1422—
1427).— The course of the reaction w ith a given nitrile cannot be predicted, but th e products are of three t y p e s : (a) dithiopiperazines (cf. A ., 1911, i, 696, 712), (b) im inonitriles (from am inonitriles), and (c) thiodeoxyhydantoins, a new class of substances.
Thus, a-am inoisobutyronitrile or a-im inodiisobutyro- nitrile in aqueous-alcoholic am m onia yields w ith hydrogen sulphide a substance, m. p. 153— 155°
{mercury salt, m. p. 175°), provisionally regarded as 5-thio-2 : 2 : 4 : ‘k-tetramethyl-2-deoxyhydantoin,
9 ®,
This shows acidic and basic pro-NH*.CMeaperti.es, is n o t desulphurised b y mercuric oxide, and is hydrolysed by acids to a-am inoisobutyric acid, a-A m in o - a - m ethylbutyronitrile, a - am ino - a-ethyl - butyronitrile, and a-im inodipropionitrile are n o t attacked b y hydrogen sulphide under th ese condi
tions. a-Am inopropionitrile yield s a-im inodipropio
nitrile w ith an unstable, oily by-product, w hilst im inodiacetonitrile yield s m ainly iminodiacetothio- amide, m . p. 124°, w ith (?) 5-thio-2-deoxyhydantoin, m. p. 186°, and an am orphous substance.
H . E . F . N o t i o n . A c tio n of c y a n o g e n b r o m id e o n d im a g n e s iu m a c e ty le n e d ib ro m id e . A. S. N e k r a s s o v (J. Russ.
Phys. Chem. Soc., 1927, 5 9 , 915— 919).— See A., 1927, 1051.
C h e la te c o m p o u n d s of t h a l liu m d ia lk y l. R . C.
M e n z i e s , N . V. S i d g w i c k , E . F . C u t c l i f f e , and J. M. C. F o x (J.C.S., 1928, 1288— 1291).— B y double decom position of thallium dialkyl halides w ith thallous acetylacetone and corresponding com pounds or by the action of thallium dialkyl ethoxide or carbonate on th e appropriate diketone, th e follow ing were prepared : thallium dimethyl acetylacetone, m . p. 214—
215° (some decom p.); thallium diethyl acetylacetone-, thallium dimethyl benzoylacetone, m . p. 128— 129°;
thallium diethyl benzoylacetone, m . p. 116— 11S°;
ethyl thallium diethyl acetoacelate, m . p. S8— 90°, and thallium dimethyl salicylaldehyde, decom p. 200°.
These are crystalline com pounds which can be sublimed under reduced pressure and are soluble in benzene and hexane, and thus appear to be chelate co-ordinated com pounds of th e ty p e
^CMe-Ox
G i l / XFlMe,. i n water, however, th ey form X JM eiO ^
ionised solutions of alkaline reaction, in w hich the thalliu m dialkyl can be titr a te d q u an titativ ely .
B. W. A n d e e s o n . C o m p le x s a l t s of ¡3 -m e th y ltrim e th y le n e d ia m in e w i t h b iv a le n t p la tin u m . F . G. M a n n (J.C.S.,
1928, 1261— 1263; cf. th is vol., 157).—A solution of (i-m ethyltrim ethylenediam ine hydrochloride in aqueous sodium hydroxide when refluxed w ith aqueous potassium chloroplatinite yielded a solution which, afte r tre a tm e n t w ith sodium brom ide, yielded bis-$-methyltrimethylenediamineplatinous dibromide, [Pt{CHMe(CH2‘N H2)2}2]Br2, m. p. 266—26S° (de
com p.). T he corresponding di-iodide, m . p. 263—
264° (decomp.), an d dinitrate (deflagrates) were sim ilarly obtained, an d from th e di-iodide th e di- d-cainphor-^-sulphonate monohydrate, m. p. 279—
2S1° (decomp.), [a] + 1 5 °, di-d-x-bromocamphor-Tc-sul- phonate, slow decomp. 278—2S5°, [a] +69-2°, and ditartrate were prepared. T he above six compounds, although highly crystalline, showed no sign of cis- iratts-isom erism ; moreover, th e la st three m entioned could n o t be resolved into optically active fo rm s ; th e observed ro tatio n s were due solely to th e sulphonate
ions. B. W . A n d e e s o n .
C o m p le x c o m p o u n d s of p l a t i n u m a n d p a l l a d i u m w i t h o rg a n ic s u lp h id e s . E . C. F b i t z m a n n (Ann. in st. platine, 1926, No. 4, 55—-179).— U n published work by Tschugaev and Ily in is reported.
T he compound 2CMe2(CH2S E t)2,2PtCl2, rose, changes a t 114— 116° to a yellow modification (monomeric), m. p . 218—219°. The compound C(CH2S E t)4,PtC l2, decomp. 235°, w hen h eated yields th e compound C(CH2S E t)4,2PtCl?, yellow, m. p . < 1 0 0°. The com
pound 2(EtSH C .'C H SEt),,2PtCl2 an d a m onomeric fo rm are recorded. I n unpublished w ork by Tschugaev an d Iv an ov , th e following compounds are re c o rd e d : PdCl„,2Et„S, yellow, in. p . 82°;
P d B r2,2E t2S, m . p. 100°; P d I2,2 E t2S, m. p. 104°;
PdCl2,(CH2S E t)2, m. p . 180°; P d B r2,(CH2S E t)2, m. p.
159°; P d I2,(CH2S E t)2, m. p. 154°. I n unpublished w ork b y Tschugaev an d M alchevski th e transitio n from th e non-conducting ty p e [P t,2 E t2S,Cl2] to th e electrolyte [P t,4 E t2S]Cl2 is traced. Tschugaev and V ladim irov (unpublished) hav e shown th a t com pounds of th e ty p e [P t,2 R2S,X 2] existing in two isom eric forms show negligible conductivity in m ethyl alcohol, fu rth e r addition of th io eth er yielding [P t,4 R2S]CI2, th e tiro com pounds being in eq ui
librium . “ C h e m i c a l A b s t e a c t s . cycZ oPentane d e r iv a tiv e s . P r e p a r a t i o n of
1 : 2-d im e th y lc y c io p e n ta n e . G. C h a v a n n e and ( M l l e . ) L. d e V o g e l (Bull. Soc. cliim. Bclg., 1928, 37, 141— 152).—Magnesium m ethy l iodide converts cycZopentanone in to 1-m e th y lc y c lo p e n ta n o l, b. p . 135-6°/760 m m ., m . p. 36° (a llo p h a n a te, m. p. 157°), d eh y d rated by p-toluenesulphonic acid to 1-m ethyl-
A1-cyclop en te n e , b. p. 75-5— 7C°/760 m m ., m. p.
-1 2 7 -2 °, d[ 0-7979, ?t'rf 1-4347. W hen this h y d ro carbon is tre a te d w ith m onochlorocarbam ide (cf.
Detceuf, A., 1922, i, 236, 327) there are formed a t least two ch lo ro h y d rin s having b. p. ab o u t 75°/
10 m m ., d f 1-1039, K 1-4785, an d m. p. 35—37°, respectively. The m ixture of chlorohydrins is con
v erte d b y tre a tm e n t w ith potassium hydroxide in to
7 4 6 BRITISH CHEMICAL ABSTRACTS.— A.
1-methi/l-Al-cyc\openiene oxide, b. p. 110-8— lll° /7 6 0 mm ., m. p. -S 0 -5 ° , df™ 0-9266, »g 1-4311, which reacts w ith excess of m agnesium m ethyl iodide to give th e same stereoisomeric m ixture of 1 : 2-dim ethyl- ci/cZopentanols as t h a t obtained from 2-methylc?/c?o- pentanone (van Rysselberge, A., 1926, 1238). W hen th e theoretical q u a n tity of th e G rignard reagent is used an d th e reaction p roduct is n o t distilled under reduced pressure th e m ain p roduct is 1 :2-dim ethyl- q/c/opentenc, together w ith a sm all am ount of
2-m ethylc;/dopentanone.
C atalytic reduction of 1 : 2-dimethylcycZopentene in acetic acid using platinum -black affords 1 :2-di- metlijdc.ycZopentane, b. p. 94—99°/760 m m ., d f 0-764, )(„ 1-417 (cf. v an Rysselberge, loc. tit.).
H . Bu r t o n. C a ta ly tic a c tio n of m e r c u r y a n d b is m u th [in n itr a tio n ] , J . B. M e n k e (Rec. trav . chim., 1928, 4 7 , 6 6 8—672).—The n itratio n of benzene by metallic n itrates under varying conditions has been studied.
W hen a m ixture of benzene vapour and nitrogen oxides is heated in an atm osphere of m ercury vapour or is passed over bism uth oxide a t 400—500°, nitrobenzene an d nitrophenol are formed. The form ation of organo-m ctal! i c compounds which occurs when m ercury is used is avoided by th e second procedure, and in this ease also, much less nitrobenzene is formed.
Benzene is n itra te d to nitrobenzene by a m ixture of acetic anhydride and cupric, aluminium, ferric, cobalt, or nickel n itra te a t 80°. Similar results are obtained w ith mercuric or m ercurous n itrate, b u t in addition a little o-nitrophenol and (different) m ercury compounds are obtained in these cases. W hen bism uth n itrate is used sim ilar results are obtained b u t no m etal complex compounds are formed. Thiophen is sim ilarly n itra te d b y the action of alum inium n itrate and acetic anhydride a t 60—65°. W hen acetic acid is sub stituted for its anhydride no n itratio n occurs except when the m ercury or bism uth salts are used, an d th en only to a sm all extent, complex m ercury compounds also being produced. Since phosphoric acid destroys its catalytic activity, bism uth cannot be used to replace m ercury in th e ordinary K jeldahl or Gunning processes, nor in th e oxidation of n a p h thalene to phthaiic acid. J . W. B a k e r .
C o m p a ra tiv e e ffe c ts of th e n itr o - , c a rb o x y l, a n d su lp h o n ic a c id g r o u p s o n th e h y d r o ly s is of a r y l h a lid e s . W. D a w e s and E . S. W o o d (J.C.S., 1928, 1122— 1131).—The com parative ac tiv ity of the chlorine atom in chlorobenzenes su b stitu ted in the 4-, 2 : 4-, and 2 : 4 : 6-positions by nitro-, carboxyl, and sulphonic acid groups, respectively, shows th a t th e order of activation of th e chlorine atom is N 02> S 03H > C 02H. The activ ity due to th e nitro- group is, however, enormously (about 1 0 3 times) greater th a n th a t due to th e other groups ; th e sulphinic acid group has an influence com parable w ith these latter. A nitro-group in the o-position also greatly increases th e effect of a carboxyl or sulphonic acid group introduced into the ^-position. The following compounds were prepared : diphenylamine- 2 : 4 : 6-irisulphonanHide, m. p. 227° (decom p.); the
■potassium salts of chlorobenzene-2 : 4 : 6-trisulphonic acid and l-chloro-2-m trobenzene-4-sulphonic acid,
respectively, and th e ammonium salt of clilorobenzene-
^»-sulphinic acid. B . W. A n d e r s o n . A c tio n of m a g n e s iu m on p - a n d m -d ib ro m o - b e n z e n e s . J . S . S a l k i n d and P. V. R o g o v i n a (J. Russ. Phys. Chem. Soc., 1927, 59, 1013— 1018).—
An experim ental refu tation of older theories th a t only one halogen atom in an arom atic dibromo-compound reacts w ith magnesium in a Grignard synthesis.
m- and ^-Dibromobenzenes were allowed to react w ith twice th e theoretical q u a n tity of m agnesium ; th e products were hydrolysed, and the ex ten t of- th e reaction was determ ined b y dissolving the m etal rem aining and m easuring th e hydrogen evolved, and also by titra tin g th e ionisable bromine. I n each case, ab out 6 6—75% of th e dihalogen magnesium derivative was formed.
The m ain pro du ct was ta r, only ab ou t 23—31%
of th e theoretical yield of benzene being obtained.
M . ZVEQINTZOV.
O x id a tio n r e a c tio n s . II . O x id a tio n of to lu e n e w ith n i t r i c a c id a n d o x id e s of n itr o g e n in p re s e n c e of o x y g en . P . A s k e n a s y , E . E lo d , and C. T r o g u s (Annalen, 1928, 4 6 1 , 109— 130;
cf. A,, 1927, 635).—W hen toluene is boiled w ith nitric acid (d 1-4?) for 1 0 0 hrs., benzoic and ^-nitrobenzoic acids are th e m ain products, together w ith some o-nitrotoluene and carbon dioxide and traces of picric acid. C ontrary to th e statem en t of F ittig (Annalen, 1861,117, 192; 120, 222), who probabty used im pure toluene, no hydroxybenzoic acids are formed. The absence of ^-nitrotoluene is due to the com paratively ready oxidation of this substance by dilute nitric acid a t a high tem perature. On th e other hand, o-nitro-toluene and -benzoic acid readily react w ith hydroxylam ine formed during th e heating process, to give o-toluidine and anthranilic acid, which undergo conversion into diazo-compounds in presence of nitrous acid. This would appear, a t any ra te , to be a source of, e.g., nitrogen and phenol and thu s of th e picric acid actually identified.
Oxidation of toluene w ith nitric acid under con
siderable pressures (cf. Sachse, G.P. 216091) h as also been investigated in detail. O xidation proceeds in definite stages an d th e tim e interv al between the beginning of reaction and th e p oint when the toluene layer sinks to th e bottom and begins to disappear w ith sim ultaneous evolution of nitric oxide has been plo tted against tem perature. Pressure as such has little effect on th e reaction, b u t in so far as it leads to th e attain m en t of a higher-boiling m ixture it has a great effect. R eaction becomes explosive a t tem per
atures above 200°. Increase in concentration of the nitric acid from 5 to 30% causes increase in yield of to ta l products, in th e am ount of carbon dioxide formed, and in the nitrogen content of th e products.
The ra te of reaction increases also, 30% acid reacting violently. A num ber of tables are given showing the effect of different conditions on th e reactions under investigation (tem perature, pressure, catalysts, etc.).
E . E . T u r n e r , A ry ls u lp h o n y l c h lo rid e s . II. E . G e b a u e r - F u l n e g g , E. R i e s z , and S. I l s e (Monatsh., 1928, 4 9 , 41— 46; cf. A., 1927, 139).—T h e action of sodium iodide on 2>-toluenesulphonyl chloride in acetone
ORGANIC CHEMISTRY. 7 4 7
solution yields sodium yj-toluenesulphinatc, di-^-tolyl- disulphone (Kohler an d M acDonald, A., 1899, i, 904), and di-p-tolyldisulphoxide (Otto and Troger, A., 1891, 718), iodine being liberated. The m echanism of form ation of these compounds is discussed. The action of sodium iodide on ^-diphenylsulplionyl chloride (obtained from the acid, which is produced in 90%
yield by sulphonation w ith concentrated sulphuric acid at- 50° in th e presence of nitrobenzene as a diluent) similarly yields sodium ^-cliphenylsulphm ate an d di-diphenyldisulphone. J . W. B a k e r .
A lte r n a tin g effect in c a r b o n c h a in s . XXV.
M e c h a n is m of a r o m a tic s id e -c h a in s u b s titu tio n . XXVI. N it r a t i o n of co-chloro- a n d w -brom o-?)- xy len e. 0. K . I n g o l d and E. R o t i i s t e i n (J.C.S.,
1928, 1217— 1221, 1278— 1280).—X XV . The side- chain brom ination of nitro-£>-xylene yields a t least 76% of 3-nitro-p-o;ylyl bromide, m. p. 76°, showing th a t the reaction m ust proceed by prelim inary a ttra ctio n of potential bromine cations by electrons. The above bromide yielded the same S-nitro-’p-xylyl-u-trimethyl- ammoniumpicrate, m. p. 138°, as was obtained through the corresponding q u aternary chloride, from the know n 3-nitro-p-xylyl chloride (m. p. 48°).
X X V I. I n the n itratio n of w-chloro- and co-bromo- p-xylene su bstitution occurs chiefly in th e position ortho to th e m ethyl group. These results are of im portance in th e developm ent of th e theory of anionotropy. A m ixture, b. p. 120°/3 mm., of 2- and '¿-nitroA-methylbenzyl ethyl ethers was incidentally obtained during the investigation.
B. W. A n d e r s o n . [ P r e p a r a tio n of] s ty re n e . T. W. A b b o t t and J . R . J o h n s o n (Org. Syntheses, 1928, 8, 84— 86).
A r o m a tic c o m p o u n d s containing- a te r t .-b u ty l g ro u p . A. E . T s c i i i t s c h i b a b i n , Si E l g a s i n e , and V. A. L e n g o l d (J. R uss. Phys. Chem. Soc., 1928, 80, 347— 354).—See th is vol., 404.
P r o d u c tio n of c o n d e n s e d r i n g s y s te m s b y c a ta ly tic d e h y d ro g e n a tio n . II . A c tiv a te d c h a r coal a s r e d u c in g a g e n t. N. D. Z e l i n s k i and M. V.
G a v e r d o v s k a j a (Ber., 1928, 61, [¿?], 1049— 1053;
cf. A., 1927, 47).—Triphenylcarbinol is converted by platinised charcoal a t 150— 1S0° in to the labile form of triphenylm ethane, m. p. 81°, and by activated charcoal a t 300° into carbon dioxide and th e stable variety of the hydrocarbon, m. p. 92°. Phenyldi- ci/c/ohexylcarbinol, m. p. 77°, in contact w ith platinised charcoal affords S-phenylfluorene, m. p. 145°, whereas with activated charcoal a t 300° it gives phenyldicyclo- hexylmethane, b. p. 210—212°/20 m m., d f 0-9S90.
Under similar conditions, diphenylm ethylcarbinol yields Q-metliyljluorene, m. p. 46°, and diphcnylethane, b. p. 268—269°, d f 0-9875, resp ectiv e^, wliilst diphenylethylcarbinol affords 9-ethyl-fluorene, m. p.
10S°, and diphenyl propane, b. p. 278—279°/759 mm.
Dim ethylbenzylcarbinol is converted into isobutyl- benzene, b. p. 170°/756 mm ., d f 0-8628, in presence of either catalyst. Phenylmethylbenzylcarbinol, b. p.
179°/14 nun., m. p. 51°, in contact with platinised charcoal gives 9-methylphenanthrene, m. p. 94°, whereas w ith activated charcoal it suffers reduction to tx$-diphenylpropane, b. p. 278°/751 mm., d f 0-9807.
M ethylethylbenzylcarbinol appears to be reduced only
to $-benzylbutane, b. p. 113— 115°/11 m m ., d f 0-868;
th e form ation of a condensed system is n o t observed.
ieri.-Amjd alcohol is converted into pentane, b. p.
30—30-5°, d f 0-62S1. Phenol is converted into benzene by repeated passage over activated charcoal a t 300°. I n general reduction of oxygenated organic compounds in presence of activated or platinised carbon occurs a t notably lower tem peratures th a n are required w ith other forms of carbon. H . W r e n .
S y n th e s is of tw o h y d r o c a r b o n s of h ig h m o l.
w t., d e r iv a tiv e s of flu o re n e a n d m e th a n e . K . D z i e w o ń s k i an d M . P a n e k (Bull. Acad. Polonaise, 1927, A , 745—751).—The action of m ethylal on fluorene in presence of phosphorus pentoxide in boiling chloroform solution yields 2 : 2'-dijluorylrnethane, m. p. 201—202°. Dinitro-2 : 2'-difliiorybnethane, m p.
256—257°, is obtained by n itration, an d oxidation by sodium dichrom ate in acetic acid yields 2 : 2'-di- jluorenone ketone, m. p. 297—298° [triphenylhydrazone, m. p. 203° (decomp.)]. Fusion of th e ketone w ith potassium hydroxide yields a t 2 0 0—2 1 0° an acid, C27H20O7, m. p. 262—265°, and a t 260—270° diphenyl- 2 : 4'-dicarboxylic acid. The form ation of th e last proves th e constitution of th e foregoing com pounds.
As a by-product in the first condensation there is form ed di( fluorylmethylfluoryl)methane,
[C6h4— c gh 3- c h2-c gh3— CgH3]2CH2
c h2 CH2 ’ m - P- - 4b~~
247°. This yields on oxidation di(fluorenonylmethyl- fluorenonyl) ketone,
m p 324—326°, which is decomposed by fusion w ith potassium hydroxide a t 280° to give an acid, C27H20O7.
R . K . C a l l o w . C lo su re of th e flu o re n e r i n g in th e d i-a - n a p h th y lm e th a n e s e rie s . O. M a g i d s o n (Trans, sci. chem .-pharm . In st., 1926, [16], 32— 48 ; Chem.
Zentr., 1928, i, 58).—See A., 1925, i, 384.
D is s o c ia tio n of p h e n a n th r e n e b y h e a t in t h e p re s e n c e of h y d ro g e n u n d e r p r e s s u r e . N. A.
O r l o v (J. Russ. Phys. Chem. Soc., 1927, 59, 895—
902).—See A., 1927, 1060.
P h o to d e c o m p o s itio n of tr ip h e n y lm e th y l. S. T.
Bow den and W. J. Jones (J.C.S., 1928, 1149—
1158).—The region of the visible spectrum in which triphenylm ethyl shows the strongest absorption, viz., th e greenish-blue (5300— 4000 A.), is th e m ost active in effecting its decomposition, ultra-violet light having little or no effect. The first products of the photochem ical change are probably trip hen yl
m ethane an d phenyldiphenylenem ethyl, the la tte r th e n undergoing association to diphenylbisdiphenyl- ene-ethane. The behaviour of the triphenylm ethyl radical is shown to be different from th a t of the tr i
phenylm ethyl ion, since th e la tte r (in liquid sulphur dioxide) is not photoehem ically reactive. The slight decolorisation noticcd in “ solid trip h en y lm eth y l”
exposed to sunlight is thought to be due to the presence of adsorbed solvent. B. W. A n d e r s o n .
H y d ro g e n a tio n of te tr a p h e n y lm e th a n e a n d y > -h y d ro x y te tra p h e n y lm e th a n e u n d e r p r e s s u r e .
V. N. I p a t i e v and B. N. D o l g o v (J. R uss. Phys. Chem.
Soc., 1927, 59,1087— 1091).—See th is vol., 163.
7 4 8 BRITISH CHEMICAL ABSTRACTS.----A.
O d o u r a n d c o n s titu tio n a m o n g th e m u s t a r d o ils [th io c a r b im id e s ] . I I I . G. M. D y s o n (Porf.
Ess. Oil Rec., 1928, 19, 171— 174; cf. this vol., 283, 514).—The odours of arom atic thiocarbim ides containing both halogen and m ethyl su bstitu en t groups together are described. The results agree w ith th e generalisation previously described. The n atu re of th e odour is dependent m ore on orient
ation th a n on th e n atu re of th e su b stitu en t group, and where chlorine and m ethyl groups occur together in th e same com pound th e effect of th e chlorine is more strongly m arked th a n th a t of th e m ethyl group. The following su b stitu ted phenylthio- carbim ides and th eir odours are described ; 3-chloro-A-methyl-, b. p. 274° ; é-chloro-3-methyl-, m. p. 22°; 2-chloro-5-methyl-, b. p. 269°; 5-chloro-2-methyl-, b. p. 272° ; 2-chloro-A-methyl-, m. p. 23° ; é-chloro-2-methyl-, m. p. 34°; 2-bromo-‘i-methyl-, m. p. 18°, and 4-bromo-2-methyl-, m. p. 32°. s-Di- (2-bromo-4c-methyl)- and s-di-(4:-bro7no-2-methyl)-thio- carbamides, m. p. 192° an d 178°, are described.
o-, m -, and jj-N itrophenylthiocarblm ides an d four of th e nitrotolylthiocarbim ides have been prepared.
W ith th e exception of th a t of iJ-nitrophenylthio- carbimide, th eir odours are very faint.
E. H . S h a r p l e s . 2 -M e th y l-5 -j'so p ro p y la n ilid e s of s o m e h i g h e r f a tty a c id s . R . M. H a n n an d G. S. J a m i e s o n ( J . Amer. Chem. Soc., 1928, 50, 1442— 1443).— Lauryl-, m. p. 82—83°; m yristyl-, m. p. 8 8—S9°; palmityl-, m. p. 90—91°; stearyl-, m. p. 93— 94°; arachidyl-, m. p. 81— 82°, and lignoceryl-, m. p. 84— 85°, 2-methyl- 5-isopropylanilides have been prepared from the appropriate acid chlorides and cymidine.
H . E . E . No t t o n. M o le c u la r d i s s y m m e tr y d e p e n d e n t o n r e s tr i c t i o n of r o t a t i o n a b o u t a s in g le lin k in g . O p tic a lly a c tiv e b e n z e n e s u lp h o n y l-8- n i t r o - l - n a p h th y lg ly c in e . W . H . M i l l s and K . A. G.
E l l i o t t (J.C.S., 1928, 1291— 1302).—Benzenesul- phonyl chloride reacts w ith 8-nitro-l-naphthylam ine in pyridine, yielding S-nilro-l-benzenesulpho'namido- naphthalene, m. p. 198— 199° {dibenzene&ulphonamido- derivative, m. p. 199°), which is converted b y ethyl brom oacetate in presence of sodium ethoxide into ethyl 'N-benzenesulphonyl-$-nitro- 1 -naplithylaminoacet- ale, m. p. 173°. H ydrolysis of this w ith dilute acetic and sulphuric acids gives N-benzenesulphonyl-8-nitro-l- naphthylylycine, NO2-C10H6-N(SO2Ph)-CH2-CO2H (I), m. p. 214°. If the ro tatio n of th e
P h S 02-N-CH2-C 02H grouping is obstructed b y th e nitro-group (cf. Mills, Chem. and Ind., 1926, 45, 884) i t is probable th a t (I) will exist in tw o enantio- morphous modifications. W hen equivalent q u a n t
ities of (I) and brucine are mixed in acetone solution brucine \-benzenesulphonyl-S-nitro-\-naphthylamino- acetate (-f-H20 ), m. p. 195— 196°, is formed. This sa lt exhibits m u taro tatio n in chloroform solution, th e average period of half change a t 15-5° being 5 m in. W hen th is salt is decomposed in chloroform solution w ith dilute sulphuric acid, th e resulting chloroform solution of th e /-acid is strongly lævo- ro tato ry , and the tim e of half change a t 14-9° is 17 min. A solution of th e brucine Z-acid salt in
boiling m ethyl alcohol gives, on cooling, brucine d - benzenesulphonyl - 8- nitro - 1 - naphthylaminoacetate ( + 3 H20), which is strongly d extro rotatory in chloro
form solution, th e ro ta tio n falling gradually to the final value of th e brucine Z-acid salt. If a chloro
form solution of (I) is tre a te d w ith a chloroform solution of brucine th e initial Isevorotation falls gradually to an equilibrium value. Decomposition in th e usual w ay indicates th e form ation of th e brucine cZ-acid salt, since th e acid obtained shows d extro
ro tation.
In order to dem onstrate th a t th e optical activity found was n o t due to th e asym m etric terv alen t nitrogen atom , benzenesulphonyl-l-naphthylglycine, m. p. 188— 189° {ethyl ester, m. p. 89°), was examined.
The quinine salt of this acid exhibited no m utarot- atio n under the conditions employed.
H . B u r t o n . O x id a tio n of a r y lt h i o l a r y lid e s . E . G e b a u e r - E ü l n e g g and E . R i e s z (Monatsh., 1928, 49, 31— 40;
cf. A., 1927, 1060).—4-Chloro-2-nitro-l-chlorothiol- benzene has been condensed w ith o-aminophenol, o- and 2>-phenylenediamines, an <l as-dim cthyl-^- phenylenediam ine, and th e action of oxidising agents on th e resulting chloronitrophenylthiolanilides has been investigated. Condensation with o-aminophenol in ether yields <i-cliloro-2-nitrophenyltJiiol-o-hydroxy- anilide, m. p. 143°, which, on oxidation w ith sodium dichrom ate and acetic acid, or w ith hydrogen per
oxide, yields 4:-cMoro-2-nitrophenyl-o-benzoquinone- thiolimine, C6H3Cl(Np¿*S*NiC<^4!0, m. p. 134—
135°. Similarly, ^-phenylenediam ine yields bis-4'- chloro-2'-nitrophenylthiol-^-phenylenediamine (I), m. p.
212°. This is converted b y various oxidising agents or b y heating w ith acetone or acetic acid into a red substance, m. p. 264— 270°, which by chlorination w ith chlorine in chloroform suspension yields
4-chloro-2-nitrobenzenesulphonyl chloride, also obtained by th e direct chlorination of (I). o-Phenylenediamine yields ¿>¿s-4'-chloro-2’-nilrophenylthiol-o-phenylenedi-amine, m. p. 181°, together w ith 2 : 3-diamino- phenazine hydrochloride. The former, b y oxidation, yields a red substance, m. p. 172°. os-Dimethyl-^)- phenylenediam ine condenses to yield -p-dimethyl- amino-4:'-chloro-2'-nitrophenylthiolanilide, m. p. 152°, which b y oxidation w ith concentrated nitric acid yields 4' - chloro -2 ' - nitrophenyl-^-benzoquinonethiol.
iminedimethylimmonium nitrate,
Cr)H3C l(N 02)-S-N:CGH4: m i e2-N 03, m. p. 1 0 2°, from which th e free base, m. p. 186°, is obtained b y the action of alcoholic am m onia. The base is also obtained when hydrogen peroxide replaces nitric acid as th e oxidising agent, th e corresponding chromate being obtained when chromic acid is used.
J . W . B a k e r . P r e p a r a t i o n a n d c o n s titu tio n of th io c a r b - a m id e s of flu o re n e . L. G u g l i a l m e l l i , A . N o v e l l i , C. R uiz, an d C. A n a s t a s i (Anal. Asoc. Quim. Argen
tin a, 1927, 15, 337— 362; cf. this vol., 629).—
Eluorene derivatives are considered to show pro
perties characteristic of 2 : 2'-disubstituted diphenyl derivatives, and m ay possess a configuration anal
ogous to th a t proposed b y K aufler for diphenyl.
T he behaviour of 2 : 7-diaminofluorene as an o-di- am ine in thiocarbam ide form ation an d th e difficulty
ORGANIC CHEMISTRY. 7 4 9
of thiocarbam ide form ation by 2-am ino-derivatives (loc. cit.) owing to steric hindrance m ay be explained on this basis.
B y reaction w ith thiocarbonyl chloride in boiling
B y reaction w ith thiocarbonyl chloride in boiling