chloride (A., 1904, i, 966) in CHC13, yields on deacetyl- ation 2 -m e th y l-6 -la c ta m id o q u in o lin e , m. p. 192° (m etho
su lp h a te ). The a c e ty l-la c ta m id o -d e n v a ,tiv e s of PhCHO, m. p. 114—115°, and of 2-methylbenztliiazole, m. p.
153—155° (m eth o su lp h a te), yield on appropriate con
densation the 2 -{p -a m in o s ty r y l)a c e ty l-la c ty l and 2-(p-
a c e ty l-la c ta m id o sty ry l) derivatives of aminobenzthi- azole methochloride. p-Aminobenzaldéhyde or nitroso- dimethylaniline with the appropriate 2-methyl- quinoline at 100° in presence of piperidine yield
2 -(j> -a m in o styryl)-6 -a cet- and -6 -la c t-a m id o q u in o lin e m ethochloride and the corresponding 2 -{p -d im e th y l- a m in o a n il) derivatives. Condensation of acetyl- lactamidobenzaldehyde with 6-amino-2-methylquinol- ine methochloride results in simultaneous hydrolysis of the Ac group, giving 2 -(p -la c ta m id o s ty r y l)-6 -a m in o - q u in o lin e m ethochloride. Similarly, 6-acetamido-2- methylquinoline methiodide yields 2-(p-la cta m id o - sty ry l)-Q -a c e ta m id o q u iiw lin e m e th io d id e . Glyceric acid, treated successively with AcCl and SOCl2, gives
d ia c e ty lg ly c e ry l ch loride, b. p. 75—85°/15 mm", which with 6-amino-2-methylquinoline and then Mel, gives
G -d ia c e ty lg ly c e ry la m id o -2 -m e th y lq u in o lin e m eth io d id e,
m. p. 217—219° (decomp.). Condensation of the appropriate benzaldehyde in MeOH with piperidine yields the 2 - ( p -a m in o s ty r y l) and 2 -(p -a c e ta m id o s ty r y l)
derivatives of 6-glyeerylamidoquinoline methochloride
(m eth io d id e), the two Ac groups of the glyceryl group being hydrolysed. 6 - R - A m in o - 2 - m e th y lq u in o lin e (m eth io d id e), where R=octoyl, nonoyl, undecoyl, and lauryl, were prepared by treating the acid chloride with 6-amino-2-m'ethylquinoline in AcOH at 100° for 1 hr. Condensation of these products yielded the
m e th io d id e s and m eth och lorides of the corresponding
2 -(p -d im e th y la m in o a n il) derivatives. None of the above anil derivatives exhibits marked trypanocidal activity; the styryl derivatives are more active.
Acétylation of the NH2 in the quinoline nucleus does not generally increase the trypanocidal potency, but occasionally tends to produce convulsive effects.
F. O. H o w u t t. Relation between constitution, colour, and reactivity of heterocyclic com pounds. Deriv
atives of hom ophthalim ide. A. Me y e r and R.
Vi t t e n e t (Ann. Chim., 1932, [x], 17, 272—411).—
Indene with Iv?Cr20 7 and hot H2S04 gives a 65% yield of homophtkalic acid and a little indanone. The prep, of homophthalimide (I) is modified. With the appropriate diazo-compound in aq. Na2C03 at 0°
2 : 4-dihydroxyquinoline affords 3-benzene-, m. p.
263—264°, -o-cU orobenzene-, decomp. 284—285°, -m- and -p-nitrobenzene-, m. p. 295—296° (decomp.) and 332—333° (decomp.), respectively, -o- and -p-toluene-,
m. p. 267—26S° (decomp.) and 268—269° (decomp.), respectively, -o- and -m -n itro -p -to lu en e-, m. p. 282—
284° (decomp.) and 312—314° (decomp.), respectively,
-m -x y le n e -, m. p. 264—265°, -1- and -2 -n a p h th a len e-,
m. p. 267—268° and 264°, respectively, -m -ca rb o x y- benzene-, m. p. 308—310° (decomp.), -a zo-2 : é -d ih y d r - o x y q u in o lin e , d i-(2 : i-d ih y d ro x y q u in o lin e -d -a z o )-p j> '- d ip h e n y l, decomp, above 320°, -d i-o -to h jl, m. p. above 320° (decomp.), and -di-o-an i& yl, decomp, above 320°. (I) yields similarly 4-benzene-, -o-chloro- benzene-, m. p. 281—283°, -o- and -p -n itro b en zen e-,
m. p. 276—277° and 290—291°, respectively, -0-,
624 B R IT IS H C H E M IC A L A B S T R A C T S .— A .
-m-, and -p-tolue7ie-, m. p. 266—267°, 228—230°, and 240—242°, respectively, -o- and -m -n itr o -p - tolu en e-, m. p. 270—272° and 305—307°, respectively, m-xylen e-, m. p. 260—261°, -1- and -2-i\aph th ale7\e-,
-m. p. 283—285° (decomp.) and 262—264°, respec
tively, -o- and -vi-ca rb o x yb en zen e-, decomp. about 315° and m. p. 305—307° (decomp.), respectively,
a 7 itip y r in e -, m. p. 252—254° (decomp.), -hom o- p h th a lim id e , d ih o m o p h th a lim id e A -a z o -p p '-d ip h e n y l,
•d ito ly l, and -d ia n is y l, decomp. above 320°, and the
N a salts of the following acids : h o m o p h th a lim id e A - a zo -b en zen e-p -su lp h o n ic, -m .-xyle7ie-o-sulphonic, -(3-
iia p h th o l-6 : 8-d isu lp h o n ic , -n a p h th io n ic , -n a p h th o l-2 : 4-
d is u lp h o n ic a c id , and -p tir h u lin e . Substantive d y e s
are produced by addition of (I) to an alkaline solution of tetrazotised benzidine, tolidine, and dianisidine, already coupled once (in both acid and alkaline solution, when different products result) with H, G, J, naphthionic, and Neville and Winther’s acid, and with benzidine already coupled once with salicylic and Schaeffer’s acid and 2-p-nitrobenzeneazo-H acid.
(I), when heated with the appropriate primary amine, gives at least 75% yields of iY-phcnyl-, m. p. 191°
(lit. 188°) [oximmo-derivative, m. p. 234—236°
(decomp.)], -p-to lyl-, m. p. 173° (cmmmo-derivative, decomp. 241—243°), -a- and -$ -n a p h th y l-, m. p. 212°
and 220°, respectively, -h o m o p h th a lim id e; these substances are fairly readily hydrolysed; the oximino- derivatives are very stable. O xim inoho77iophthalim ide
decomposes at 242—243°. By means of Mel or EtI and hot KOH-EtOH were prepared ~N-phenyl -
4 : i-di77iethylho7nophthali77iide, m. p. 149—150°, N-
p h e n y l-, m. p. 146°, N-p-to ly l-, m. p. 177—178°, and N-a-naphthyl-, m. p. 224°, -4: 4=-diethylhom oplithal- i m i d e; these substances have no physiological action.
Coupling at 0° with diazotised NH2Ph gives 4-
ben zen eazo-'N -ph en yl-, -p-to lyl- (m. p. 258—259°), -a- and -p-7la p h th y l- [m. p. 283—284° (decomp.) and 262—
263°, respectively] -h o m o p h th a lim id e. By treatment with the appropriate NO-compound in warm EtOH were prepared p - d im e th y la m in o p h e n y l-, m. p. 243°,
p -d ie th y la m in & p h e n y l-, m. p. 196—197°, a n tip ijr y l-,
m. p. 224—225°, p - to ly la n tip y r y l- , m. p. 227—228°
(decomp.), -in m io p h th a lo im n id e , C6H4<^^q^^]>CO ,
a n lip y ry lp h O u ilo n -'N -p h e n y l-, m. p. 210°, -p-to lyl-,
m. p. 223—224°, -a- and -$-naphthryl-, m. p. 239—240°
(decomp.) after sintering at 235°, and 180—181°
(decomp.), respectively, - im id e ; these substances are red or bluish-violet, are decomposed rapidly by dil. alkali or acid or by prolonged boiling in neutral solvents, and are immediately reduced by boiling aq. Na2S20 4. By means of the appropriate aldehyde and a few drops of piperidine or NHEt2 in hot EtOH were prepared N-p h e n y l-, m. p. 193—194°, N-p-
to ly l-, m. p. 185—186°, N-a- and -$ -n a p h th y l-, m. p.
225° and 204°, respectively, A -b e n zy lid e n e h o m o p h th a l- im id e , Fd-phenyl-, m. p. 244—245°, N-p-to ly l-, m. p.
245—246°, N-a- and -$ -n a p h th y l-, m. p. 141° and 159—
160°, respectively, A -p -d im e th y la m in o b e n z y lid e n e -
homophthaliTTiide. The antipyryliminohomophthal-
imides with hot 15% HC1 give 85—90% yields of phthalonimide (II), m. p. 228—229° (lit. 224°),
p h th a lo n -p h e n y l- (III) (m. p. 220—221°, sublimes from 215°), -p-to lyl- (IV) (m. p. 238°, sublimes from
220°), -a -n a p h th y l- (V) [m. p. 239—240° (decomp.) after sintering from 200°], and -$ -n a p h th y l- (VI) [m. p.
268—269° (decomp.)] -im id e ; these substances dis
solve in alkali giving (probably) phthalonic acid and substituted phthalonamides. The phenylhydrazones of these phthalonimides are identical with the products of coupling (I) with diazotised NH2Ph ; the following derivatives of the phthalonimides are described:
(II) p h e n y lm e th y lh y d ra zo n e , m. p. 242-5°, and oxime,
decomp. 242—244° ; (III) p h en yh n eth ylh yd ra zo n e,
m. p. 204°, o x im e , m. p. 234—236° (decomp.), and
sein ica rb a zo n e, m. p. 230—231° (decomp.); (IV)
pliem jhneth7jlliydrazo7ie, m. p. 199°, o x im e, decomp.
241—243°, and sem icarbazo7ie, decomp. 236—237°;
(V) and (VI) phe7iyhnethijlhydrazo7ie, m. p. 212° and 199—200°, respectively. o-Pbenylenediamine in hot EtOH gives p h e n a zirie derivatives with (II) (m. p.
267°), (III) (m. p. 23S—239°), and (IV) (m. p. 232—
233°).
The colours of the above compounds are discussed and considered to be in accord with analogy. The azo-dyes are considered to have the azo- rather than the hydrazone structure, excepting those from (I) itself, which are considered to be thermolabile mixtures of both forms. R. S. Ca i i n.
Determination of constitution of bases ob
tained from protein. III. CJ0H14O„N2. F.
W r e d e (Z. physiol. Chem., 1932, 206, 146—154;
cf. this vol., 284).—The base C10H14O2N2 (I) (A., 1931, 245) when boiled for a short time with dil.
HC1 loses 1 mol. of AcOH and forms dl-3 -acetainiio-2 -h o m o p ip e rid o n e , ^j%.^^j2.coJ^>CH-NHAc, m. p.
163°, which on longer boiling (4 hr. with 10% HG1) gives dHysine and 1 mol. of AcOH. d-Lysine by Troensegaard’s method, or on heating the dihydro
chloride with AcOH and AcCl to 100°, yields (I), which is therefore C H 2% q ^ ^%-CMe.
d-Ornithine similarly gives a co77ipou7id, CgH^Odh
(chloroaurale, darkens at 175°, m. p. 184°); which on hydrolysis yields df-3-acetamido-2-piperidone and finally ornithine. J. H. Bi r i o n s h a w.
Derivatives of 4 : 5-diketopyrazoline. E. D.
Ch a t t a w a y and A. Ad a i r (J.C.S., 1932, 1022—
1026; cf. A., 1927, 776).—2 : 5-Dichlorophenyl- liydrazine hydrochloride and dihydroxytartaric acid give diketosu cci7iic a c id 2 : 5-dichlorophe7njlosazone
(I), m. p. 195° (decomp.), converted by Ac20 into the a n h y d r id e , m. p. 233°. Diketosucci7iophe7iyl- h y d r a z id e 2 : o-dich loroph eru jlosazon e, m. p. 286°, is obtained from the corresponding anhydride and NHPh-NH2. (I) or its anhydride and EtOH-HCl form E t 4 : o - d i k e l o - l - ( 2 ' : 5 '-dichlorophe7iyl)pyrazohm -
‘¿ -ca rb o x yla te 4-(2" : 5" -dich loroph en ylh ydrazo7ie) (II).
m. p. 213° [a c id , m. p. 214° (decomp.)], also obtained by the action of EtOH-HCl on E t diketosuccinate, 2 : 5-dichlorophe7iylosazo7ie, m. p. 207°, which may be prepared from the corresponding h ydrazon e, m. p.
101° (formed by the action of Et oxalacetate on diazotised 2 : 5-dichloroaniline). D ik eto su ccin ic acid
2 : 4 : 5-trich loroph en ylosazcm e and its arih ydride, m. p.
295—300°, are similarly prepared. Diazotised tn- chloroaniline and Et oxalacetate afford the hydrazone,
O R G A N IC C H E M IS T R Y . 62 5
converted into E t d ik eto su ccin a te 2 : 4 : 5-trich loro- p h en ylo sa zo n e, m. p. 224°, forming with EtOH-HCl, 4 : 5- dilceto -1 - (2' -: 4 ': 5' - tr ic h lo r o p h e n y lfp y r a z o lin e -i-
(2" : 4" : 5 " -tric h lo ro p h e n y lh y d ra zo n e ), m. p. 308—
310° (decomp.), with elimination of the C02H group.
C a rb e th o x y g ly o x a l-2:4:5-Irich loroph en ylh ydrazon e, m. p.
118°, prepared from diazotised trichloroaniline and Et sodioformylacetate, gives the osazon e, m. p. 242°, which cannot be hydrolysed; the corresponding
ca rb o x yg lyo x a l-2 : 4 : 5-trich lo ro p h en ylo sa zo n e, m. p.
284°, is obtained from dibromopyruvic acid and 2 : 4 : 5-triclilorophenylhydrazine hydrochloride.
F . R. Sh a w.
Fission of the glyoxaline ring in a base C9H3 4ON3 prepared from protein. F. Wrede and G.
Fetterriegel (Z. physiol. Chem., 1932, 205, 198—
200; cf. this vol., 284).—The compound, m. p. 185°, formed by the action of m-nitrobenzoyl chloride on the base CgHjjON, (A., 1931, 245) is 4-[(3y-di-(m-
n itro b e n za m id o ) - A& - p r o p e n y l\ - 2 : 5 - d im e th y lo za zo le .
BzCl similarly yields 4 :-[(iy-d i(b en za m id o )-b P -p ro p -
e n y l]-2 : 5 -d im e th y lo x a zo le , m. p. 172° (cf. Windaus, A., 1910, i, 283). The presence of a glyoxaline ring in the base is thus confirmed.
J. H. Be r k i n s h a w .
Chloroaurates of histamine and glyoxaline.
F. H o r n (Z. physiol. Chem., 1932, 207, 1 1 1 —112).—
When ordinary histamine chloroaurate, B,2HAuC14, is dissolved in hot H20 and rapidly cooled, an irregular
ch loroau rate, B^AugClg, sinters 165—166°, decomp.
179—182°, is formed. This seems to be a charac
teristic of the glyoxaline ring, since ordinary iminazole chloroaurate, B,HAuC14, on similar treatment gives an irregular ch loroau rate, B,AuC13, decomp. 190°.
j ! H. B i r k i n s h a w.
Substituted piperazines. I. 2 : 5-Dimethyl- and tetramethyl-piperazines. II. Bistetra- methylenepyrazine and bistetramethylenepiper- azine. M . Go d c h o t and M . Mo u s s e r o n (Bull. Soc.
chim., 1932, [iv], 51, 349—360, 360—372).—I. Reduc
tion of 2 : 5-dimethylpyrazine by H2 in presence of Ni at 150—155° affords the a- or trans-piperazine, m. p.
118°, and no trace of the cis-compound, but in presence of Pt a small amount of cis- is also formed, a similar result being obtained when oximinoacetone is hydrogenated with Pt as catalyst. Tetramethvl- pyrazine cannot be reduced in presence of Ni, but with Pt two tetramethylpiperazines, m. p. 38° and 69—70° {c ld o r o p la tin a ta; p ic r a te , m. p. about 170°) (cf. Kipping, A., 1930, 223), are obtained, the same products resulting from reduction of oximinomethyl Et ketone.
II. The following salts of bistetramethylenepyrazine (I) have been prepared : h yd ro ch lo rid e (+ H 20 ) ; h y d ro brom ide (-f3H20 ) ; h y d r io d id e (-f-3H20 ) ; su lp h a te
(+2H20 ) ; o x a la te; ta r tra te , decomp. 190°; citra te,
decomp. 200°; benzoate, decomp. 190°; sa licyla te', chloroaurate (-j-3H20); m e r c u r ic h lo r id e ; and chloro- sta n n a te. Reduction of (I) with Na and EtOH gives
b iste tra m e th y le n e p ip e ra zin e , m. p. 132—133°, also obtained by hydrogenation in presence of Al-Hg and of Ni, but with Pt two stereoisomeric p ip e r a z in e s ,
in. p. 105—106° (dimfraso-derivative, m. p. 182°), and m. p. 62—63° (dmitroso-derivative, m. p. 107°), result. Reduction does not take place with Et20
and Na, Sn and HC1, and SnCl2. It is suggested that isolation of the three isomerides is connected with the multiplanar configuration of the 6-membered
rings. F. R. Sh a w.
Mechanism of the formation of indigotin in the von Baeyer synthesis. L . Ta n a s e s c u and A.
Ge o r g e s c i t (Bull. Soc. chim., 1932, [iv], 51, 234—
240).—Condensation of o-N02-CnH4-CHO with PhAc in presence of Na3P04 gives P h $ -o -n itr o p h e n y l-$ - h y d ro x y e th y l ketone, (II), m. p. 108—109° \ B z deriv
ative (I), m. p. 152°], also obtained together with Ph o-nitrostyryl ketone by using alkali in place of Na3P04 (cf. A., 1902, i, 879). (I) and (II) with Zn and AcOH at 100° give 2-phenylquinoline. (II) with Zn and AcOH at 0° followed by treatment with FeCl3 gives a su b sta n ce, m. p. 121°, probably o-nitrobenzoyl- acetophenone. The action of light on Me 3-o-nitro- phenyl-[l-hydroxyetliyl ketone (improved prep.) in pyridine gives a su bstan ce, m. p. 170°, and in EtOH a su b sta n ce, m. p. 150° (previous softening). Similar results are obtained with the Bz derivative and with (I) and (II), formation of indigotin being observed
in some cases. A. A. L e v i.
Preparation of 7 : 7'-dimethyl- and 5 : 7 : 5 ': 7'- tetramethyl-8 : 8'-diquinolyl. H. P. W a r d and M. G. W a r i n g (J. Amer. Chem. Soc., 1932, 54, 1697).—2-Iodo-3-nitrotoluene and Cu give 6 : 6'-di- nitrodi-o-tolyl, which is reduced and then converted (Skraup) into 7 : T -d im e th y l-8 : 8'-d iq u in o ly l, m. p.
213—215°. 5 : 7 : 5 ' : T -T e tr a m e th y l-S : S'-d iq u in o ly l
is similarly prepared from 4-iodo-5-nitro-m-xylene.
C. J. W e s t (b ).
Reactions of allantoxanic acid and allant- oxaidine with alkali hydrogen sulphites. J.
Bou g a u l t and (Mlle.) Pi n g u e t (Compt. rend., 1932, 194, 979—981).—A mixture of aq. solutions of alkali allantoxanate or allantoxaidine and alkali H sulphite affords an additive product. These products are de
composed by mineral acids and by I, affording allant
oxanic acid and allantoxaidine. The following are described : C4H204M,MHS032H20 and
C3H302N3,MHS03,H26 (M =K or Na).
J. L. D ' Si l v a. Preparation of dimethylalloxantin. H. Bi l t z and P. N a c h t w e y (Ber., 1932, 65, [B ], 565—567).—
Contrary to Biilmann and Mygind (A., 1930, 1193), the method of Biltz (A., 1913, i, 166) is trustworthy for the prep, of dimethylalloxantin from theobromine.
Reduction of methylalloxan by SnCl2-HCl must be effected slowly at 0°. II. W r e n.
Chlorophyll. XX. Conversion of chlorin e trimethyl ester into deoxypyrrophmophorbide.
H. Fi s c h e r and H. Si e b e l. XXI. Conversion of deoxophylloerythrin and phyUoerythrin into chloroporphyrin e5 ; chloroporphyrin e4. H.
Fi s c h e r, J. H e c k m a i e r, and J. Ri e d m a i r (Annalen, 1932, 494, 73—86, 86—100).—XX. Chlorin e Me, ester (I) boiled with Na2C03 and pyridine for 72 hr.
gives 37% of unchanged (I) and 10% of d e o x y p y rr o - ph ceoph orbide (II), m. p. 230° (o x im e), which appears to be identical with the product similarly formed (much more readily) from phaeophorbide a . (II) is a (mono) Me ester, is unaffected by Na2C03 and pyridine, is reduced by EH in AcOH at 55° to
phyllo-6 2phyllo-6 B R IT IS H C H E M IC A L A B S T R A C T S .— A .
erythrin, and is oxidised by 02 and MeOH-KOH in EtOH-pyridine to a ehlorin (reduced by HI to rhodo- porphyrin). Chlorin e7 (III) {C u salt) with Na2C03 and pyridine gives much unchanged (III) and a porphyrin similar to chloroporphyrin e 5. (Ill) and moist Ag20 in boiling EtOH afford a s a lt,
C35H360 6N4Ag (reduced to porphyrins showing the spectra of chloroporphyrins e5 and ee), whilst (I) gives a sa lt, C37H40O6N4Ag.“ Conant and Hyde’s method (A., 1930, 225) of decarboxylating methylphaeophorb- ide affords pyrroporphyrin and phylloerythrin and not a pyrrophoeophorbide. The phase test with all deoxypyrrophaeophorbides is negative. The produc
tion, by ring closure, of (II) from (I) is strong evidence for the authors’ formula for (I).
XXI. Deoxyphylloerythrin (IV) (and phyllo
erythrin) with 20% oleum at room temp, for 42 hr. give chloroporphyrin e5 (formylrhodoporphyrin) (V); after 24 hr., (IV) affords small amounts of (IV) and (V) and phylloporphyrinsulphonic acid.
(V) crystallises from Et20 in two forms [data by
St e i n m e t z], Condensation products could not be obtained from chloroporphyrin e4 Me (F e and C u
salts) or Me, esters {F e and C u salts) with Et2C03, CH(OEt)3, HC02Et, Et2C204, CH2(C02Et)2, or C0(CH2-C02Et)2 (rhodo- and phyllo-porphyrins are generally formed), or with PhCHO, p-N02'C6H4*CH0, or p-NO-CGH4-NMe2 [the production of (V) is deter
mined spectroscopically], Chloroporphyrin e4 is oxid
ised to (V) by short treatment with cold 20% oleum and by 0 2 and MeOH-KOH in EtOH-pyridine; its conversion (by ring closure) into phylloerythrin could not be effected. H. Bu r t o n.
Derivatives of setioporphyrin I. H. Fi s c h e r
and W. N e u m a n n (Annalen, 1932, 494, 225—245).—
AEtioporphyrin I (I) [Z n , in. p. (Pregl block) 343°,
N i (+0-5C5H5N), m. p. (block) 327°, Co, m. p. (block) 337°, A g , and complex S n salts; K „ derivative, formed from (I) and K in xylene and dry C02, whereby only 1 atom of H is produced] and Br (20 mol.) in boiling AcOH give a c o m p o u n d , C32H33N4Br8, converted by dissolution in AcOH-HC02H and pptn. -with H20 into a su b sta n ce, C32H3503N4Br3, and by treatment with COMe2 into an O-containing co m p o u n d containing about 2 Br per mol. (I) in AcOH-HCl treated with H20 2 at about 40° gives the d ih yd ro clilo rid e (-}-COMe2) (II), m. p. (block) 250°, (tube) 290° (not sharp), of
tetra ch lo ro cetio p o rp h yrin , decomp. 400° (block) without melting. (II) and pyridine at 30° afford dichlorocetio- p o r p h y r in (III), m. p. 331° (d ih yd ro ch lo rid e), whilst at the b. p. (I) is regenerated. Direct chlorination of (I) gives (III); a monockloro-derivative could not be prepared. The conversion of (II) into setio- xanthoporphyrinogen by Pb02 indicates that sub
stitution of the p-side-chains does not occur. (I) and an excess of H ,02 in AcOH-HCl give a co m p o u n d ,
Ci„H12O10C1. (I) and aq. NaNO, in cone. H2S04 below 70° give a d in itr o n itro so c e tio p o rp h y r in , un
affected by H20 2 in H2S04 at —5°, and apparently also formed (spectrum) from dihydroxysetioporphyrin
{C u salt), aq. NaN02, and H2S04.
[By A. Tr e i b s. ] (I) and HN03 {d 1-4) give a
n itro c e tio p o rp h y rin , m. p. (block) 2S7° [C u salt, m. p.
(block) 325°], also formed with HN03 {d 1-48) and
carbamide. In another case, using HN02-free HN03
(d
1-48),dinitrocetioporphyrins,
m. p. 301°{Cu
salt,m. p. 325°) and 293°, resulted. (I), HN03
{d
1-48),and NaN02 give a
trinitroœtioporphyrin,
m. p. 293°{Cu
salt, m. p. 316°), spectroscopically identical with the (N02)3-compound previously described (A., 1928, 1382). (I) and NaNO, in Ac0H-H2S04 afford anitro-compound,
C32H3604Nfi, m. p. 275°{Cu
salt,m. p. 321°). In the above cases, nitration is probably accompanied by oxidation.
(I) and Et„0-MgMeI give œ tio p h y llin ,
C32H36N4Mg(+MeOH), m. p. (block) 347—349°
(erystallographic data given), which with picric acid in Et20 affords the dipicrate of (I). The catalytic reduction of (I) and œtiohæmin is investigated;
(I) absorbs 6H with colloidal Pt in AcOH+10% HC1 at 36°, but under similar conditions, ætiohæmin is not reduced. The A g salts of mesoporphyrin Me, ester and protoporphyrin are described.
H. Bu r t o n. Ring synthesis of porphyrins with substituted and unsaturated side-chains. III. Synthesis of a-5-carbethoxy-2 : 4-dimethyl - 3 - pyrrylsuccinic acid. H. Fi s c h e r, P. H a r t m a n n, and H. J. R i e d l (Annalen, 1932, 494, 246—263).—Et 2 : 4-dimethyl- pyrrole-5-carboxylate and acetylenedicarboxylic acid at 110° give
5-carbethoxy-2
:d-dimethyl-Z-pyrrylmaleic acid,
m. p. 257° (decomp.), reduced by 3% Na-Hg and I120 at 3—5° to the 5-Et
ester, m. p. 240° (decomp.), of
a-ô-carboxy-2
:4,-dimethyl-H-pyrrylsuccinic acid,
m. p. 172—173° (decomp.).Et 2 : 4-dimethyl-3-pp-dicyanovinylpyrrole-5-carb- oxylate (A., 1924, i, 543) and aq. KCN in EtOH give (after acidification) the alkali-sol. E t 2 : i-d im e th y l-3 - a $ $ -tr ic y a n o e th y lp y r ro le -5 -c a rb o x y la te (I), m. p. 163°, hydrolysed by 1% NaOH (about 3 mois.) to 3-formyl- 2 : 4-dimethylpyrrole-5-carboxylic acid (II) and by EtOH-HCl to a 5 -ca rb eth o x y-2 : A -d im eth yl-3 -p y r r y l
su c c in ic a c id m o n o n itr ile , m. p. 185° {M e ester, m. p.
166°). (I) and Br in boiling MeOH afford E t 2:
4-d im e th y l-3 -o .$ $ -tric y a n o v in y lp y rro le -5 -c a r b o x y la tc , m. p.
194°. Me(2) Et(5) 4-methyl-3-p3-dieyanovinylpyrrole- 2 : 5-dicarboxylate and KCN similarly give the 3-app-
tr ic y a n o e th y l derivative, m. p. 167°, hydrolysed by 66% NaOH to 3 -f o r m y l-i- m e th y lp y r r o le -2 : 5-dicarb- o x y lic a c id , decomp. 260°. Et 2 : 4-dimethyl-3-p- cyano - ¡3 - carbethoxyvinylpyrrole - 5 - carboxylate and KCN afford E t 2 : A d im eth yl-3 -a .fi-d icya n o -$ -ca rb eth o x y- e th y lp y rro le -5 -c a rb o x y la te , m. p. 108°, hydrolysed by EtOH-HCl to the 3-a(or [3)-q/awo-(3(or a)-carboxy-$- ca rb eth o x yeth yl derivative, m. p. 183°, by 1% NaOH to (II), and by EtOH-KOH to 2 : i-dim ethyl-3-?>- c y a n o -$ -c a rb o x y v in y lp y rro le -5 -c a r b o x y lic a c id , m. p.
240°, or its 5-E t ester, m. p. 241°, according to the amount of KOH used. Et 3-formyl-2 ; 4-dimethyl- pyrrole-5-carboxylate (III) does not react with CH2(C03H), in EtOH-NH2Ph ; the a n il, m. p. 138°, of (ÏII) (converted by KCN into E t 2 : é-d im eth yl-3 - a n ilin o c y a n o m e th y lp y rro le -D -c a rb o x y la te , m. p. 133°) is produced. 2 : 4-Dimethyl-3-(3J3-dicyanovinylpyrrole and KCN give 2 : i-d im eth yl-'à -o .$ $ -tricya n o eth ylp yrro le,
m. p. 1SS° ; 2 : 4-dimethyl-3-p-cyano-(3-carbethoxy-vinylpyrrole-5-carboxylic acid similarly affords the
Z -v.$ -d icya n o -$ -ca rb eih o x yeth yl derivative, m. p. 180°, hydrolysed (alkali) to (II). 2 :4 D m e th y l3 P P
-O R G A N IC C H E M IS T R Y . 627
d ic y a n o v in y lp y r ro le -D -c a rb o x y lic a c id , m. p. 204°, is obtained from (II) and GH2(GN)2 in EtOH-NH2Et at 65°. Et 2 : 4-dimethyl-3-aa-dicarbethoxyethylpyrrole-5-carboxylate and carbamide in EtOH-NaOEt at 105—
110° give (5 -carbeth oxy-2 : < i-d im e th y l-3 -p y rry l)m e th y l- b a rb itu ric a c id , m. p. 240°; with EtOH-NH3 at 130°, a m o n o a m id e , m. p. 191°, results.
Carboxyhsematic acid, obtained by oxidation of wouroporphyrin II with Cr03 in dil. H2S04, has m. p.
154° (decomp.) (cf. A., 1927, 1088), and is identical with the “ natural ” acid. H. Bu r t o n.
Constitution of bile pigments. VII. 1' iEtio- mesobilirubin ’' and the nature of the Gmelin reaction. H. Fi s c h e r and E. A d l e r (Z. physiol.
Chem., 1932, 206, 187—200; cf. A., 1931, 1420).—
5-Bromo-4 : 3 ': 5'-trimeth}d-3 : 4'-diethylpyrrometh- ene hydrobromide when heated with KOAc in AcOH yields 5-hydroxy-4 : 3 ': 5 '-trimethyl-3 : 4'- diethylpyrromethene (I). Treatment of (I) with CH2Br-C02H equiv. to 2 mols. of Br gives a mixture of hydrobromides from which there were isolated:
p r o d u c t A , C3;H3G03N4, dark violet plates, Gmelin reaction negative, but gives blue colour; p r o d u c t B ,
C31H3802N4, emerald-green needles, m. p. 263—265°, Gmelin reaction positive; p r o d u c t C , C31H3802N4, bluish-violet prisms, m. p. 253° [trih y d ro b ro m id e (II), violet plates, Gmelin reaction positive, Zn(OAc)2 reaction positive]. Reduction of (II) with Zn dust in AcOH gives cetio m eso b iliru b in , C31H40O2N4, Gmelin reaction as for mesobilirubin. If the Gmelin reaction with mesobilirubin is interrupted at the blue phase the CHC13 solution gives the same Zn(OAc)2 reaction as (II). Condensation of neobilirubic acid with p -
nitrobenzaldehyde in 25% aq. HC1 affords p-n itro - b e n zy lid e n e n e o b iliru b ic a c id , m. p. 252° (corr.), with
p - dimethylaminobenzaldehyde, p - d im e th y la m in o - b e n zy lid e n e n e o b iliru b ic a c id , m. p. 282°, positive Gmelin reaction. The pigments isolated probably correspond with the various colour phases of the Gmelin reaction.
A bilirubin prep, from liver echinococcus on analysis gave figures corresponding with the C33 bilirubin formula. J. H. Bi r k i n s h a w.
Bile pigments. XI. Ferro- and glauco-bilin.
H. Fi s c h e r, H. Ba u m g a r t n e r, and R. H e s s (Z.
physiol. Chem., 1932, 206, 201—210; cf. A., 1931, 497).—Mesobilirubin with FeCl3 in hot AcOH gives
fe r r o b ilin (I), CoaH^O^FeCl^IICl, m. p. 260°
(decomp.) [M e 2 ester (II), m. p. 255° and m. p. 244°].
With NaOH (I) gives g la u c o b ilin (d eh yd ro m eso b iliru b in )
(III), sinters at 205—220°, m. p. 304° (decomp.)
[M e2 ester (IV), violet, m. p. 216°, or blue, m. p. 222°].
With aq. Na2C03, (II) yields (IV). FeCl, reconverts (III) into (I), (IV) into (II). In a sealed tube at 215° for 5 min. (Ill) gives mesobilirubin. Reduction of (III) or (I) with Na-Hg gives mesobilirubinogen.
Reduction of (III) with Zn dust in MeOH affords a su bstan ce, C33H40O6N4,0-5CHCl3 (from CHC13), blackening at 230—240°, m. p. 280° (decomp.).
Heating mesobilirubin for 6 hr. in conc. H2S04 at 100° or in boiling HC02H gives (III). Neoxantho- biliiubic acid in boiling HC02H also gives (III). A second fe r r o b ilin ( ?), C37H460 6N4,FeBr3,HBr, m. p.
228°, is obtained from mesobilirubin by the action of HBr and FeBr3 in HC02H. J. H. Bi e k i n s i i a w.
Uteroverdin, the green pigment of the dog's placenta. R. Le m b e r g and J. Ba r c r o f t (Proc. Roy.
Soc., 1932, B, 110, 362—372).—U te ro v e rd in h y d r o ch loride, the extraction of which is described, in abs.
MeOH-HCl gave the M e ester, C35H33.420 6N4, m. p.
199° (corr., decomp.), which contains 20Me and is not identical (optical examination) with the Me ester of oocyan (A., 1931,1066). The two pigments, however, give a similar Gmelin reaction and show similar absorption (acid and neutral solution). Uteroverdin, C^H^-ggOgN.}, is provisionally given a structural formula based on that for bilirubin (ib id ., 1420).
F. O. Ho W IT T . Constitution of cytochrome. K . Ze i l e (Z.
physiol. Chem., 1932, 207, 35—47).—Repeated reduction and oxidation of htcmin or amorphous haematohsemin in pyridine with Na2S204 and K 3Fe(CN)G, respectively, gives a hsemin insol. in pyridine, sol. in neutral and slightly acid aq. media.
It resembles cytochrome, but differs in that the porphyrin obtained by elimination of Fe is insol. in Et20. Treatment of the product obtained by the action of HBr-AcOH on natural hsemin with glycine Me ester gives a co m p lex , C40H48O8N G, m. p. 164°
(corr.), similar in spectroscopic properties and solu
bility to cytochrome C and its corresponding por
phyrin. It could not, however, be converted into an Et20-sol. porphyrin with HBr-AcOH.
J. H. BmKINSHAW'.
Interaction of ammonium and alkylammon- ium sulphides with aqueous formaldehyde.
Interaction of ammonium and alkylammon- ium sulphides with aqueous formaldehyde.