prepared by direct condensation of the components
O R G A N IC C H E M IS T R Y . 751
in cone. HC1 and treatment with 20% HC104. Those salts are all intensely coloured and give rise to colour bases (treatment with NaOAc) and .¿-bases (Na2C03).
Absorption spectra of these salts, in the visible region, are plotted; that of 4'-amino-3 : 7-dihydroxyflavylium chloride (description reserved) in 1% HC1 closely resembles those of betanin and the pigment of A t r i p le x
h o r te m is . An improved prep, of 2-hydroxy-4-meth-
oxybenzaldohyde from p-resorcylaldchyde is described.
J. W. B.
Constitution of p-naphthapyrones. B. B. D e y ,
B. H. R. R a h , and Y. S a n i c a r a n a r a y a n a n (J.
Indian Chem. Soc., 1932, 9, 71—77).— ¡3-Naphthol arid malic acid in H2S 04 (cf. A., 1884, 1346) give CO, a s u b s ta n c e , m. p. above 320°, and 1 : 2-pa- naphthapyrone, m. p. 118° (A., 1883, 1136).
P-Naphthol, Na succinate, and succinic anhydride at 180° give 1 : 2-(3a-naphthapyrone-3-acetic acid (this vol., 519) ( M e ester, m. p. 149°), and 3 : 3-d i- 1: 2 - ^ a - n a p h lh a p y r o n c , m. p. 345°. A. A. L.
Synthesis of rotenone and its derivatives. II.
Synthesis of r issic and derric acids, and the con
stitution of rotenone, deguelin, and tephrosin.
A. R o b e r t s o n (J.C.S., 1932, 1380— 1388).— 2-Hydr- oxy-4 : 5-dimethoxybenzaldehyde, CH2Br-C02Et, and K„C03 in C0Mea give E t 2 - a l d e h y d o A: 5-d im e th o x y - p H en o x ya c eta ie (I), m. p. 129° (s e m ic a r b a z o n e , m. p.
189°), oxidised by KMn04 in aq. COMe2 to the 2-c a rb -
oay-derivative, m. p. 190°, which is hydrolysed to 2-carboxy-4 : 5-dimethoxyphenoxyacetic (rissic) acid (Takei, A., 1931, 490; La Forge, i b id . , 1415), m. p.
257—258° (decomp.) (lit. 256° and 261—263°).
Hippuric acid, (I), NaOAc, and Ac20 at 100° (bath) give the corresponding a z la c to n c , m. p. 175°, hydro
lysed to 2-c a r b o x y m e th o x y -4: 5- d im e th o x y p h c n y lp y r u v ic a c id , m. p. 238° (decomp.) (darkens slightly at 220—
225°), which is oxidised by alkaline H202 to 2-carboxy- methyl-4 : 5-dimcthoxyphenoxyacetic (derric) acid (La Forge and Smith, A., 1930, 782, 1187; La Forge, loc.
cit.). 2-Carboxy-, 2-carboxy-4-methoxy-, and 3 : 4-di-
methoxy-phenoxyacetic acids are prepared (as above) from CH2Br-C02E t and Me salicylate, Mo 4-0-methyl- Q-rcsorcylate, and 3 : 4-dimethoxyphenol (improved prep, given; cf. A., 1931, 73), respectively, with subsequent hydrolysis.
A structure is assigned to rotenone; this is identical with that proposed by La Forge and Haller (this vol., 401). The formation of dehydrorotenone (¡sofiavone typo) is analogous to the transformation of a fiavanone into a flavone, and the hydrolysis of dehydrorotenone to derrisic acid is analogous to the decomp, of an isoflavone. Formulae are proposed for tephrosin and
deguelin. H. B.
Vegetable, fish, and insect poisons. TV. Con
stituents of varieties of D e r r i s and T e p h r o s i n .
[Constitution of deguelin, tephrosin, and to x i
carol.] A. B u t e n a n d t and G. H i l g e t a g . V.
Constituents of m asterw ort (I m p e r a t o r i a o s t r u - t h i u m ) . A. B u t e n a n d t and A. M a r t e n (Annalen, 1932,495,172—1 8 6 ,1S7—210).—IV. Deguelin, teph
rosin, and a s u b s ta n c e , m. p. 231°, are isolated from the leaves of T e p h r o s ic t v o g e lii, whilst “ rotenone- resin ” (the non-cryst. part of the extract of the root of D e r r is e ll i p t i c a) contains a c o m p o u n d , m. p. 228-5°,
deguelin, and toxicarol. From work carried out largely by Clark (A., 1931, 1298, and previous abstracts), deguelin is represented as (I) (R = H ), thus differing from rotenone by containing an a-pyran (A) in place of the dihydrofuran ring. Tephrosin is represented by (I) (R =O H ).
//
“ a II ^OMe(IV.) c o2h
Toxicarol and 30% H202 hi 5% EtOH-KOH give
to x ic a r ic a c i d (probably II), m. p. 210° (decomp.), reduced (H2, P t0 2, EtOH) to netoric acid (this vol., 619), and converted by E t nitrite and conc. HC1 in EtOH into dimethyliesculctin (?). Toxicarol and 20% EtO H -K OH in MeOH at room temp, give 35% of to x ic a r o l h y d r a te (III), C23H2108 (?), m. p.
223-5° ( A c derivative, m. p. 178°), which is unaffected by hot 20% EtOH-KOH and is converted by E tO H - Conc. HC1 into dehydrotoxicarol, m. p. 233—234°
(acetate, m. p. 235—236°) (cf. Clark, A., 1931, 1065), also obtained by reduction of iododehydrotoxicarol with Zn and AcOH. Reduction (H2, Pd-charcoal) of toxicarol in EtO H -K OH gives a c o m p o u n d ,
G21IJ21O7 (?), m . p. 217-5° ( A c derivative, m. p. 192°), also formed by reduction (H2, P t 0 2, AcOH) of (III) and from dihydrotoxicarol and 20% EtOH-KOH.
Toxicarol, E t nitrite, and AcOH-conc. HC1 afford toxicarolone, m. p. 283—284°. Toxicarol is probably (IV).
V. Osthol, C15H1603 (Herzog and Krohn, A., 1910, i, 124), contains one OMe and a lactone group, has the properties of a coumarin, is reduced (H2, Pd-black, EtOAc) to d ih y d r o - o s tlio l, m. p. 83° [also formed together with a small amount of an a c id , C1BH20O4, m. i>. 8 8°, by catalytic reduction (Pd-C) in aq. KOH], and is oxidised by Cr03 in cold AcOH to COMe2 and o s th o lic a c id , C12H10O5, m. p. 255° ( M e ester, m. p. 155°). Ostruthin, CjgH^Og (von Gornp- Besanez, A., 1874, 907; 1877, i, 717; Jassoy, A., 1890, i, 1154; Herzog and Krohn, lo c . c it.) , contains one OH and a lactone group and is methylated (diazo- methane) to m e th y lo s tr u th in , m. p. 55°. This is oxidised by Cr03 in AcOH at 100° (bath) to an a ld e h y d e , O j^ H ^ , m. p. 255—256° [ o x im e , m. p. 228°
(decomp.)], oxidised further to m e th y lo s tr u th in ic a c id ,
Cu H80 5, m. p. 268°, which when heated at 270° in C 02 is decarboxylated to a c o m p o u n d , C10H8O3 (prob
ably 5 - m e th o x y c o u m a r in ) , m. p. 172°. Constitutions (I) and (II) are assigned (provisionally) to osthol and ostruthin, respectively.
OhX,h / 'V / % &h^[ch2]3-c m c :c h /\/ ’\
MeO!
(I-) ( H . )
Oxypéucedanin (IH), most probably C10H u O5 (cf.
7 5 2 B K I T I S H C H E M IC A L A B S T R A C T S .— A .
lieut, A., 1875, 772; Herzog and Krohn, lo c. c it .) ,
has in. p. 142°, and contains OH, CH20,!, and lactone groups. (I ll) boiled with 1% H 20 20 4 gives oxy- peucedanin hydrate (IV), m. p. 136° (cf. A., 1910, i, 124) [acetate, in. p. 139°, from (III) and boiling AcOH or from (IV) and Ac20-p yrid in e; d ia c e ta te , m .p . 136°, from (III) or (IV) and Ac20-N aO A c; b e n z o a te , m. p.
172— 172-5°; p h e n y lu r e th a n e , m. p. 174°]. (I ll) is isomerised at 250°/higli vac. or by boiling 10% H 2S 0 4 to ¿sooxypeucedanin, m. p. 148° (o x im e , m. p.
186°), probably thus : C12H 70 4-CH(0H)-CMe!CH2— ->
C12H 70 4-C0-CHMe2. (IV) is oxidised by Cr03 and
composition, and probably also formed using ZnCl, as the condensing agent. An indophenine (not obtained pure) is produced using hot AcOH -H 2S04 for the condensation; 2-th io to le n - b r o m o in d o p h e n in e is similarly prepared, as are i r i s - 2 : 3 -th io x e n y lb is o x in d o le ,
I s a
Mecold aq. AcOH to COMe2 and o x y p e u c e d a n in ic a c id ,
CjoHgO«, m. p. 265° ( M e ester, m. p. 185°) : C12H 70 4-CH(0H)-CMe2-0H — >C12H 70 4-C 0 ,H + COMo2. This acid is reduced catalytically to an oily product, but is not affected by Zn and AcOH (or alkali) or Na and E tO H ; decarboxylation could not be effected. (I ll) is assigned (provisionally) the constitution
CH„:CM e-CH(OH)-CH:CH/\/ 'S
\ \ A >
h 2c - o 0
Details of the isolation of (I), (II), and (III) (which are all optically inactive) from the rhizome are given.
H. B.
Thiophen series. XXIII. Thioetkers of thio-p hen. W. S t e i n k o p f and P. L e o n h a r d t (Annalen, 1932, 495, 166—171).—E t succinate (1 pt.) heated with P 2S3 (2,pts.) gives small amounts of thiophen, 2-ethoxythiophen [isolated as a d i( c lilo r o m c r c u r i) -
derivative], and (mainly) 2 - e th y lth io ltk io p h e n , b. p.
196— 1979 [isolated through its 5 - c h lo r o in e r c u r i- d c r iv -
ative (I), m. p. 140°, and regenerated by distillation of (I) with HC1]. (I) and N al in COMe2 afford H g d i - ( 5 - e t h y lt h io l - 2 - th i e n y l ) , m. p. 76°. 2 - M e th y lth io l- th io p h e n , b. p. 181-5— 183-5°, is similarly obtained from Me succinate; its 5 - c h lo r o m e r c u r i- d e n v a ,tix e ,
m. p. 168°, and N a l in COMe2 give H g d i- ( 5 - m e th y l- th i o l- 2 - t h i e n y l) , m. p. 149—150°, which with HgBr2 and H g l2 in COMe2 affords 5-b r o m o -, m. p. 153°, and 5-io d o -, m. p. 105— 107°, - m e r c u r i- 2 - m e th y lth io lth io -
p h e n , respectively. H. B.
Thiophen series. XXII. Indophenine. II.
W. S t e i n k o p f and H. H e m p e l (Annalen, 1932, 495, 144— 165).—The blue product obtained from dithienyl and isatin under the conditions previously used (A., 1931, 104) is not an indophenine (cf. Heller, i b id . ,
369), but is probably b is - a .-d ith ie n y lo x in d o le ( I ; in this and other formulae, R = NH <^|^% >C7); (I) is not reducible (vat). The condensation of mono- and di-methyl- and 2-acyl-thiophens with isatin and bromoisatin is investigated; when indophenines are produced, they are designated, e .g ., 3 : 4-thioxen- indophenine (from 3 : 4-thioxen and isatin), and 2-thiotolen-bromoindophenine (from 2-thiotolen and bromoisatin). Many of the results are contrary to those of Schlenk and Blum (A., 1923, i, 1235).
2-Tliiotolen, isatin, and H 2S 0 4 (d 1-82) in cold C6H 6 give t r is - 2 - th io to le n y lb is o x in d o le (II), olive-green, which when heated with much CH2Ac-C02E t passes into a yellowish-brown s u b s ta n c e of (probably) the same
(I)
M.
Mel
iMe Me]
R
J _R
-( I I . )
S
M e
-R Me Mi
Me ( I I I . )
typo (II), 2 : 3 - th io x e n - b r o m o in d o p h e n in e , b is - 2 :5-
tii.io x e n y l- ( 3 ) - o x in d o le , and t r i s - 2 : 4 -th io x e n y lb is o x in d o k
(III), from the requisite components. 3 : 4-Thioxen and bromoisatin in cold H 2S 0 4-C 6H 6 give 3 : 4-thioxen- b r o m o i n d o p h e n in e ; with isatin, tris-3 : 4-thioxenylbis- oxindole or 3 : 4-thioxen-indophenine (neither de
scribed) is produced. 2 : 4- and 2 : 5-Diplienylthio- phens do not condense with isa tin ; the 3 : 4-derivative gives a complex, non-reducible product. T liio p h m -
~ N -m e th y lin d o p h e n irie is obtained from thiophen, N-
methylisatin, and H 2S 0 4 in cold C6H 6. E t isatin-iY- acetate, m. p. 135° (lit. 114°), prepared from sodio- isatin and CH2Br-C02E t or from the acid chloride and EtOH, is brominated in AcOH to E t brom oisatm -
N-a c e ta te , m. p. 141— 142°, also obtained from sodio- bromoisatin and CH2Br-C02Et. These esters react with thiophen in A c 0 H -H 2S 0 4 forming th io p h e n -lST-
c a r b e th o x y m e th y lin d o p h e n in e and th io p h e n -b ro m o -N - c a r b e th o x y m e th y lin d o p h e n in e . The last-named has
M 710, confirming the previous suggestion (loc. cit.)
that an indophenine results by loss of 2 mols. of H20 from 2 mols. of isatin and 2 mols. of the thiophen.
Indophenine formation occurs with 2- or 3-mono- and 2 : 3 - and 3 : 4-di-substituted thiophens, but not with 2 : 4- of 2 : 5-derivatives. These results disprove Schlenk and Blum’s (lo c. c it .) and Heller’s (loc. cit.)
dithienyl structures for indophenine, which must possess the structure previously proposed (A., 1931, 104) or (IV) (which is assigned to the indophenines from 2-substituted thiophens). The ultra-violet absorption curves of solutions of thiophen-indophenine (V) and 2-thiotolen-bromoindophen
ine (type IV) in conc. H 2S 0 4 are very similar and differ somewhat from those of 3 : 4-thioxen-bromo- indophenine (slightly) and mesoxophenine. The ease of formation of (V) (improved prep, given) supports the previously proposed formula for (V) (and its analogue from 3-thiotolen).
2-Acetothienone, isatin, and H 2S 0 4 (d 1-82) in AcOH at 140—150° give 2a c e to th ie n o n e in d o p lie n in e -s u lp h o n i c a c i d; 2 - p r o p io th ie n o 7 ie - in d o p h e n in e s u lp h o m c a c i d (containing some disulplionic acid), 2-isovalero- th ie n o n e - in d o p h e n in e , and t h ie n o n e - i n d o p h c n in e d i s v l- p h o n i c a c i d ( B a salt) are similarly prepared. T h i e n o n e
is best obtained from 2-thienoyl chloride, thiophen, and A1C13 in CS2. Thiophen, alloxan, and SnCl4 i n
AcOH give an i n d o p h e n in e , C16H 80 6N4S2, whilst
( I V . )
O R G A N IC C H E M IS T R Y . 7 5 3
tliioplibhen, isatin, and A c 0 H -H 2S 0 4 afford t r is th io -
■y h th e n y lb is o x in d o le. The ■product, C24H 160 3N 2S2, from Mg 2-thienyl bromide and isatin is converted by heat
ing with BzOH, o-0H-C6H4-CO2H, or o-C6H 4(CO)20 into (V), a solution of which in AcOH undergoes autoxidation in sunlight to the d i s u l p h o x id e d i h y d r a t e .
An apparatus for the analysis of the N H 4 salts produced by reduction of various of the above indophenines by N a2S20 4 in aq. NH3, is described.
Indophenines giving brown vats have one CO reduced, whilst those affording red vats have both CO groups
reduced. H. B.
Indigoid dyes derived from phenanthraquin- one. I. Thionaphthenphenanthreneindigotin.
P. C. D u t t a (J. Indian Chem. Soc., 1932, 9 , 99— 101).
—3-Oxythionaphtlien in AcOH and a little HC1 con
denses with suitably substituted plienanthraquinones to give the 9'-, m. p. above 290°, and 4'- n itr o - , m. p.
above 290°, 2 ': 7'-, m. p. above 290°, and 4' : 5'-
d in itr o-, m. p. above 290°, 2'-b r o m o -, m. p. 279°,
d ib ro m o -, m. p. above 295°, d ib r o m o n itr o-, m. p. above 300°, d ib r o m o d in itr o - , m. p. 281°, 2'-, m. p. above 295°, and 4'- a m in o - , m. p. above 300°, 2 ': 7'-, in. p. above 300°, and 4 ': 5'- d i a m i n o - , m. p. above 295°, 2'-, m. p.
200°, and 4' - h y d r o x y - , m. p. above 300°, and 2 ': 7'-
d ih y d r o x y - , m. p. above 300°, -derivatives of 2-thio- naphthen-(?)9'-phenantbreneindigotin (Pummerer and Luther, A., 1931, 738). Dyeing properties of these compounds are described. A. A. L.
Preparation and dinitration of 1-phenylpiperid- ine. R. J. W. Le E é v r e (J.C.S., 1932,1376— 1379).
—Dinitration of 1-phenylpiperidine (I) with H N 0 3
(d 1-5) at —10° gives the 2 ': 4'-dinitro-derivative (yield about 90%) and proceeds byw ay of the 4'-NO„- compound [the only product isolated by nitration of
(I) with HNOg (d 1-5) in AcOH-Ac20 ]. (I) is obtained in 50% yield (by the usual method) from its 2'-NH2-
derivative but only in small amount from the 4'-iso- meride. (I) could not be prepared from piperidine and the Ph esters of p-CBH 4Me-S 0 3H, H3P 0 4, AcOH, BzOH, o-OH-CBH 4-C02H, and o-0Ac-C6H4-C02H or KPhS04. Piperidine and o- and p-nitrophenyl p-toluenesulphonatcs give p-toluenesulphonpiperidide and o- a n d p -N 0 2'C6H4‘0 H , respectively. Piperidine and P h i under pressure and thermal decomp, of benzeneazopiperichde in solvents give unsatisfactory or negative results, whilst successive treatment of piperidine with NaNH 2 (in boiling xylene) and P hi affords a little (I). 1-Chloropiperidine and MgPhBr or MgPhI react violently to give Ph2 and a little basic
off. H. B.
Preparation of l-phenyl-lutidone-3-carboxylic acid. H. K on d o and K. N akajim a (Ber., 1932, 65, [B], 791—792: cf. Limpach, A., 1931, 851).—Et P-anilinocrotonate and E t acetoacetate in presence of liquid paraffin and a little SnCl4 at 180— 190° give 4-keto-l-phenyl-2 : 6-dimethyl-l : 4- dihydropyridine-3-earboxylic acid (decomp. 267—268°) in more than 20% yield { M e ester, m. p. 209°). In absence of SnCl4 reaction occurs at 220° with production of much
resin. H. W.
Syntheses by m eans of m agnesylpyrroles.
XV. True thioindoxyl [3-thiolindole]. B. Od d o and Q. M ingoia (Gazzetta, 1932, 62, 299—317).—The
name thioindoxyl is considered more suitable for 3-tliiolindole than for 3-oxythionaphthen. The reac
tion product of magnesylindole and S when treated with BzCl gives S- b e n z o y l- 3 -th io lin d o le (I), m. p. 157°
{ A g derivative), di-indolyl sulphide, and S - b e n z o y l- 2 - th io lin d o le (II), m. p. 128° { A g and b e n z e n e a z o -deriv
atives). Both (I) and (II) on alkali fusion give BzOH and N H 2-C6H4-C02H. When AcCl is used the products are regarded as 1 : S - d ia c e ty l- 3 - th io lin d o le , m. p. 129—
130°, S - a c e ty l- 3 - th io lin d o le , m. p. 208—210° { A g deriv
ative), & -a c e ty l-2 -th io lin d o le , m. p. 184° ( A g and
b e n z e n e a z o -derivatives), and l - a c e ty l - 3 : 1 ' - d i- i n d o l y l
s u lp h id e , m. p. 95—96°. Aq.-alcoholic KOH hydro
lyses (I) to 3 - th io lin d o le (true thioindoxyl), m. p. 235°
( H g n derivative). This is insol. in cold alkali, and stable towards 0 2 in alkaline media, to mild acid oxidising agents, and to hot alkaline oxidising and reducing agents; KM n04 in C5H 5N gives not 3 : 3'- dithio-indigotin but 2 : 3 - d i h y d r o - 3 - i n d o l y l s u lp h o x id e ,
CH - N H 0 ’ m - P 248—250°. p -N 0 2-C6H4-CH0 gives
3 - th io - 2 - j> - n itr o b c n z y lid e n e in d ö lin e , m. p. 170°; there is no reaction with acenaphthenequmone or with isatin. Hydrolysis of (II) gives 2 - th io lin d o le , m. j j .
148— 150° ( 2 - th io - 3 - p - n itr o b e n z y lid e n e in d o lin e , m. p.
183°; no reaction with isatin).
Magnesylpyrrole, S, and BzCl give a black infusible
insol. product. E. W. W.
Preparation of 5 ; 7-di-iodoisatin. W. C.
S u m p t e r and L. A m u n d s e n ( J . Amer. Chem. Soc., 1932,54,1917— 1918).—5 : 7-Di-iodoisatin is obtained in about 10% yield by the method of Kalb and Bcrrer (A., 1925, i, 160), and in 60% yield from 5 : 7 : 5 ' : 7'- tetraiodoindigotin and Cr03-H N 0 3. C. J. W. (b)
Racem isation of acetyl-i-tryptophan. V. d u
V i g n e a u d and R. R. S e a l o c k (J. Biol. Chem., 1932, 96, 516—517).—Acetyl-Z-tryptophan is racemised by addition of AcaO to its solution in A-NaOH at 35—
40° (cf. A., 1929, 431), and hence acetylation of Z- tryptophan using excess of Ac20 by Berg’s method (A., 1930, 243) gives a c e t y l - d \ - tr y p t o p h a n (I), m. p.
205—206°. If only 2-54 mols. Ac20 and 5-82 mols.
NaOH per mol. of Z-tryptophan are used a c e ty l-1-
t r y p to p h a n ^ m i p. 189—190°, [aj] + 2 9 ° in aq. NaOH ((Z-a-CHPhMe-NH2 saZZ.m.p. 192— 194°, [a]g +20-6°), is obtained. This is confirmed by resolution of the d l-
compound with rf-CHPhMe-NIIo, the d-CHPhMcNH,
s a lt, m. p. 194— 196°, [a]D 19-6°, of a c e ty l- d - t r v v t o p h a n , m. p. 189— 190°, [a]S —30-2°, separating.
J. W. B.
N ew dicyclic im ine, rsogranatanine. G. K o m p - p a (Ber., 1932, 65, [B], 792—793).—Hexahydroiso- phthalic acid is dissolved in aq. NH 3, the solution Ls evaporated, and the residue distilled, thereby yielding h e x a h y d r o is o p h th a lim id e , m. p. 185— 186°,
"which is electrolytically reduced to i s o g r a n a ta n in e
[3 : 5-t r i m e t h y le n e p i p e r id i n e \ , m. p. 144— 146° [hygro
scopic h y d ro c h lo rid e -, p ic r a te , m. p. 215—217° (de- eom p.); c h lo r o p la tin a te , m. p. 195° (decomp.)].
Owing to the ease of hydrolysis of the imide, the yield of base is only 17%. H. W.
Quinoline derivatives. XXXVIII. Synthesis of [substituted]
3-hydroxy-2-phenylquinoline-4-7 5 4 B R I T I S H C H E M IC A L A B S T R A C T S . A .
carboxylic acids. H. John (J. pr. C h e m ., 1932, [ii], 1 3 3 , 259— 2 7 2 ; cf. th is v o l., 623).— I s a ti n , p h e n a c y l b ro m id e , a n d h o t 3 3 % a q . KOH g iv e 3- h y d ro x y -2 -p h e n y lq u in o lin e -4 -c a r b o x y lie a c id (I), m . p . 207°. P h e n a c y l c h lo rid e g iv e s p o o r e r y ie ld s of (I) a n d th e io d id e g iv e s t r a c e s . B y u se o f t h e a p p r o p r ia t e s u b s t i t u t e d is a t i n a n d / o r a c e to p h e n o n e d e r iv a tiv e s t h e fo llo w in g d e r iv a tiv e s of q u in o lin e -4 -c a rb o x y lic a c id w ere p r e p a r e d : 6-cMoro- (m . p . 211°),
6-bromo-(m . p . 185°), 6-iodo- (m . p . 195°), 6-methyl- (m . p . 193°), 6 : 8-dibromo- (m . p . 187°), a n d 6 : 8-dimeihyl-
(m . p . 1 5 5 °); Z-hydroxy-2-phenyl- ; Z-hydroxy-2-p-
cliloro- (in. p . 169°), -p-bromo- (m . p . 152°), a n d -p-
iodo- (m . p . 161°) -•phenyl- ; 3
-hydroxy-2-p-iolyl-(m . p . 180°), -2-(4’-diphenylyl)- (m . p . 161°), a n d -2-
mesityl- (m . p . 1 7 4 °); 6-chioro- (m . p . 191°) a n d 6-iodo- (m . p . 228°) -Z-hydroxy-2-p-chlorophenyl- ; 6-
bromo- (m . p . 220°) a n d 6 : 8-dibromo- (m . p . 208°) -3-
hydroxy-2-p-bromophenyl- ; 6-iodo-Z-hydroxy-2-p-iodo-
(m . p . 182°) a n d -p-bromo- (m . p . 240°) -phenyl- ;
6-bromo-Z-hydroxy-2-diplienylyl-,m.p.214c° ; Z-hydroxy-2-p-tolyl-6-methyl-, m . p . 212° ; 6 : Z-hydroxy-2-mesityl-8-dimethyl-, m . p . 202°. M a n y in o rg . s a lts o f t h e a b o v e a c id s w e re p r e p a r e d . T h e p re p s , of to -b ro m o a c e to m e sity le n e , co-brom o-p-iodo- (m . p.
101°), a n d -p-phenyl- (m . p . 95°) -a c e to p h e n o n e w ere
m o d ified . R . S. C.
Acridine. IX. Sim ple synthesis of acridone and 3-substituted acridones. K. L e h m s t e d t (B e r., 1932, 6 5 , [2?], 834— 839).— o -N itro b e n z a ld e h y d e slo w ly r e a c ts w ith C r>H fl, P h M c , o r h a lo g e n o b e n z e n e s i n p re s e n c e of co n c. H 2S 0 4 c o n ta in in g a l i t t l e N a R 0 2 a t ro o m te m p , y ie ld in g a c rid o n e s a n d s m a ll a m o u n ts o f d a r k , s p a rin g ly sol. p r o d u c t s ; P h N 0 2, N P h E t 2, a n d B z O H d o n o t r e a c t (cf. B a m b e rg e r, A ., 1909, i, 510). T h e fo llo w in g a r e d e s c rib e d : a c rid o n e , m . p . 3 4 7 ° ; 3 -m e th y la e rid o n e , in . p . 3 1 2 ° ; 3-Jluoroacridone,
m . p . 3 7 2 °; 3 -c h lo ro a e rid o n e , m . p . a b o v e 390° [ b y p r o d u c t 4 -c h lo ro -2 '-n itro b e n z o p h e n o n e , m . p . 151°
(co rr.)], c o n v e r te d b y su c c e ssiv e t r e a t m e n t w ith N P h M e , a n d P 0 C 1 3 in to Z-chloro-6-p-dimethylamino- ph-enylairidine, m . p . 238— 2 3 9 °; 3-bromoacridone.
H . W .
H etero-ring form ation from anilino-deriv- atives of succinosuccinic ester. G . P . P e h d s e a n d S B u t t ( J . I n d ia n C hem . S oc., 1932, 9 , 67—
70).— C o n d e n s a tio n of E t s u c c in o s u e c in a te w i t h m-
to lu id in e (cf. A ., 1928, 289) g iv e s E t 2 :5-di-m- toluidinoeyc\ohexadiene-\ : 4:-dicarboxylate, m . p . 143°.
S im ila rly a r e o b ta in e d Et 2 : o-di-o-. m . p . 122°, a n d
Et 2 : 6-di-p-hydroxyanilino-, m . p . 113°, E t 2 : 5-di- p-acetylanilino-, m . p . 119°, E t 2 : 5-di-p-acetylamino- anilino-, m . p . 179°, a n d Et 2 : 5-di-l : 3 : 4t-xylidino- cyclohexadiene-1 : 4,-dicarboxylate, m . p . 155°. A c tio n of N a O E t (or i n so m e c a se s o f N a O H ) o n th e s e a n d sim ila r c o m p o u n d s g iv e s t h e 1 :1 7 - , m . p . 255°
(d e c o m p .), 2 :1 8 - , m . p . 258°, a n d 3 : 1 9-dimethyl-,
m , p . 212°, 1 : 17-, m . p . a b o v e 260°, a n d 3 :1 9 -
dimethoxy-, m . p . a b o v e 260°, 1 :1 7 - , m . p . a b o v e 260°, a n d 3 : 19-diethoxy-, m . p . 218°, 1 : 18 : 3 :1 9 -
tetramethoxy-, m . p . a b o v e 280°, 1 : 2 : 17 : 1 8 , m . p . a b o v e 260°, a n d 3 : 4 : 1 9 : 2 0-diphenylene-, m . p . a b o v e 260°, 1 :1 7 - , m . p . 236°, a n d 3 : 1 9-dihydroxy-,
m . p . 205°, 3 : 1 9-diacetamido-, m . p . 212°, a n d
3 : 1 9-diacetyl, m . p . 158°, d e r iv a tiv e s of 6 : 9 -
dihydro-5 :22-dihydroxyacriquinoline, m . p . above 280°. A b s o r p tio n s p e c tr a m a x . a r e r e c o rd e d for t h e l a t t e r g r o u p o f c o m p o u n d s . A . A . L.
Action of diazo-com pounds on butadiene. E.
M u l l e r a n d 0 . R o s e r ( J . p r . C h em ., 1932 [ii], 133, 291— 304).— B u ta d ie n e (I) a n d a lip h a tic diazo-com - p o u n d s g iv e f irs t d e r iv a tiv e s o f v in y lp y ra z o lin e and la t e r o f d ip y ra z o lin e . W h e n k e p t w ith d ia zo m e th a n e in E t 20 f o r 2 d a y s , (I) y ie ld s 5-vinylpyrazoline, b. p.
5 0 ° / l l m m ., u n s ta b le (picrate; chloroplatinate), the c o n s titu t io n o f w h ic h is p r o v e d b e c a u s e (a) th e aq.
s o lu tio n g iv e s th o p y r a z o lin e r e a c tio n w ith wood- s h a v in g s , (6) i t is tr a n s f o r m e d b y C l2 in CHCJ3 into 4 - chloro - 5 - a(3 - dichloroethylpyrazoline hydrochloride,
h y g ro sc o p ic , m . p . 109°, a n d (c) p ro lo n g e d action of d ia z o m e th a n e in E t 20 g iv e s 5 : 5'-dipyrazoline (II),
C H < N — § H ~ ~ ] , m . p . 138°, u n s ta b le [hydrochlor
ide, s ta b le , m . p . 1 7 6 °; picrate, m . p . 174° (decom p.);
chloroplatinate^) o x id is e d b y a lk a lin e K M n 0 4 to P P '-d ih y d ro x y a d ip ic a c id . W i th C l2 in CHC13 (II) g iv e s a m ix t u r e of h y d ro c h lo rid e s , m . p . 210° (decomp.), p r o b a b ly C GH 7N 4C13 a n d C 0H 6N 4C14. W i th diazo- e t h a n e (I) g iv e s s im ila rly Z-methyl-5-vinylpyrazolinc,
b . p . 5 5 ° / l l m m . (picrate; chloroplatinate), tran s
f o rm e d slo w ly b y d ia z o e th a n e i n to 3 : 3 '
-dimethyl-5 : -dimethyl-5'-dipyrazoline, m . p . 69° [hydrochloride, m . p.
169° ( d e c o m p .) ; chloroplatinate]. W h e n h e a te d with E t d ia z o a e e ta te f o r 4 d a y s a t 100°, (I) y ie ld s EL
5 : 5'-dipyrazoline-3 : 3'-dicarboxylate ( I I I ) , m . p . 195°
(d e c o m p .), a n d 1 : 1'-dicyclopropane-2 : 2 '-dicarboxyl
ate, b . p . 6 0 °/1 2 m m ., a lso fo rm e d b y p r o lo n g e d heating o f ( I I I ) [c o rre s p o n d in g acid, a n oil (Na s a lt) ]. (Ill) y ie ld s t h e dihydrazide, m . p . 245° (d ec o m p .) [dibenzyl idene c o m p o u n d , m . p . 280° (d e c o m p .) ; diazide],
a n d o n h y d ro ly s is g iv e s t h e c o rre s p o n d in g acid, an oil, w h ic h a t 150° in v a c . g iv e s C 0 2 a n d 5 :5 '-
d ip y ra z o lin c . R . S. C.
Preparations of uracil-4-acetic and orotic acids. Orotic acid as the possible intermediate in the synthesis of purines from histidine. G. E.
H i l b e r t ( J . A m e r. C h e m . S oc., 1932, 54, 2076—
2083).— U ra c il-4 -a c e tic a c id (I) is -o b tain ed from c a rb a m id e , c itr ic a c id , a n d o le u m (1 5 % S 0 3). I t is h y d ro ly s e d b y a q . B a (O H ) 2 t o t h e Ba s a lt of P- c a r b a m id o g lu ta c o n ic a c id , w h ic h w ith HC1 regener
a t e s (I). O x id a tio n o f (I) w ith a lk a lin e K 3Fe(CN)6 g iv e s K o r o ta t e . C a ta ly tic r e d u c tio n o f th e E t ester o f (I) g iv es Et d:\6-dihydrcmracilA-acetate, m . p . 155—
1 5 6 °; sim ila rly , 3 - m e th y lu ra c il g iv e s Z-methylA : 5-
dihydrouracil, m. p . 175— 176°. T h e possibility t h a t o r o tic a c id is a n in te r m e d ia te in th e synthesis o f p u r in e s fro m h is tid in e is d isc u sse d . C. J . W . (6)
Stereoisom eric 2 : 3 : 5 : 6 - tetramethylpiper - azines. III. Reduction products of
2
: 3 : 5 : 6- tetram ethylpyrazine m ethiodide. E . B. K i p p i x g (J .C .S ., 1932, 1336— 1 3 4 2 ; cf. A ., 1931, 851).—R e d u c tio n ( H 2, P t - P t 0 2, m o is t E tO H ) of 2 : 3 : 5 : 6- t e tr a m e th y lp y r a z in e m e th io d id e g iv e s (m ainly) th e
hydriodide, m . p . 161— 162°, of t h e hygroscopic y -2 : 3 : 4 : 5 : 6 (o r 1 : 2 : 3 : 5 : 6)-pentamethylpiper- azine ( I) , b . p . 20 1 — 202°, m . p . 4 — 5° [morwhydrate,
m . p . 73— 7 4 ° ; dihydrochloride, m . p . a b o u t 300°;
O R Q A N IC C H E M IS T R Y . 755
d ih y d r io d id e , m. p. 240° (decomp.) ; p h e n y ltliio c a r b -
a m id e , m. p. 154° ; 1 -NO-derivative, b. p. 155— 157°/15
mm., m. p. 24—25° (h y d r o c h lo r id e); P- to lu e n e - s u lp h o n y l derivative, m. p. 124° (h y d r o c h lo r id e), also formed by méthylation (Mel or CH20 ) of I-p-toluene- sulphonyl-y - 2 : 3 : 5 : 6 - tetramethylpiperazine (A., 1930, 223)], and a little of an isomeride (II) (phenyl- thiocarbamide, m. p. 122— 123°), separable through its p-toluenesulphonyl derivative, m. p. 99— 100°.
(II) has not been correlated with any Me4 base.
Méthylation (CH20 ) of (I) (as hydrochloride) gives y-1 : 2 : 3 : 4 : 5 : 6-hexamethylpiperazinc, b. p. 211—
212° [ d ih y d r o c k lo r id e ; m e th io d id e , m. p. 272—274°
(decomp.)], whilst (II) similarly affords a hexamethyl- piporazine [ m e th io d id e , m. p. 275° (decomp.)].
Méthylation (Mel or CH20) of 1-p-toluenesulphonyl- (3-2 : 3 : 5 : 6-tetramethylpiperazine [4-JVO-derivative, m. p. 153— 154°, reduced (Al-Hg, aq. EtOH) to the 4-NH2-derivative, m. p. 140— 141° ( h y d r o c h lo r id e )]
gives the p-toluenesulphonyl derivative, m. p. 100—
101°, of d l -(3-2 : 3 : 4 : 5 : 6-pentamethylpiperazine
(p h -e n y lth io c a rb a m id e , m. p. 95°). dZ-(3-l : 2 : 3 : 4 : 5 :6- Hexamethylpiperazine, b. p. 203—204° (from the corresponding Me4 base and C H ,0), affords a m e th - io d id e, m. p. 275° (decomp.), whilst a-1 : 2 : 3 : 4 : 5 : 6- hexamethylpiperazine, b. p. 198—200° (e th io d id e), from the Me4 base dihvdrochloride and 40% CH20 at 160— 180°, gives a d im e th io d id e , m. p. 272—273°
(decomp.). H. B.
Pyrim idines. CXXVII. Structure of convi- cine. H. J. F is h e r and T. B. J o h n so n (J. Amer.
Chem. Soc., 1932, 54-, 2038—2045).—The presence of convicine (I) in broad beans ( V i c i a f a b a ) , reported by Ritthausen (A., 1881, 1158), is confirmed. Hydro
lysis of (I) with GA-H2S 0 4 gives alloxantin, N H 3 (1 mol.), and glucose. Oxidation with KC103 gives carbamide but no guanidine. (I) does not react with KCNO to form a carbamide. The following structure is proposed for (I) :
I---0 ---1 N H -Ç O
OH H OH I ÇO ÇH-OH,H20 H G -H .e-ç-6 — ç — ç — ç-n— c:n h
' H H OH H H
G. J. W. (b).
Pyrim idines. CXXVIII. Rearrangem ent of 2-ethylthiol - 6 - tbiocyano - 4 - m ethylpyrim idine into its thiocarbim ide m odification. Y. F. Cm and Y. H. Chen (J. Amer. Chem. Soc., 1932, 54, 2056—2059).—2 - E th y lth io l- G - th io c y a n o A - m e th y lp y r im -
id in c, b. p. 155— 158°/5 mm., m. p. 69—70°, obtained
from the corresponding chloropyrimidine and KSCN, rearranges when heated with EtOH at 100° or (boiling) xylene to 2 ^ e th y lth io l- 6 - th io c a r b in iid o A - m e th y lp y r im -
id in e (Ï), b. p. 146—158°/1 mm. (decomp.) ; prolonged
beating gives a pofymeric f o r m , m. p. 108—109°.
(I) and cone. aq. N H 3 in E t20 give the G -th io ca rb -
amido-derivative, m. p. 229—231°; with N H 2Ph, the G - p h e n y lth io c a r b a m id o - d e iiv & tiv o , m. p. 209—
210°, results. (I) and MeOH and EtOH give the corresponding th io u r e th a n e s , m. p. 84—86° and 97—
98°, respectively. C. J. W. (6) New r e a c t i o n o f c e r t a i n d i a z o s u l p h o n a t e s d e r i v e d f r o m ( 3 - n a p h t h o l - l - s u l p h o n i c a c i d . X . P r e p a r a t i o n o f p h t h a l a z i n e d e r i v a t i v e s f r o m
4-am inoazobenzene and 4'-nitro-4-4-am inoazobenz- ene. F. M. R o w e and F. S. T o m l i n s o n (J.C.S., 1932,1118—1125; ef. this vol., 404).—N a (3-naphthol-1-sulphonate and azobenzene-4-diazosulphate give benzeneazobenzene - (3 -n a p h th o l-1 - diazosulplionate, converted by Na2C03 into Na l-(benzeneazobenz- eneazo)-P-naphthaquinone-l-sulphonate, which with NaOH gives N a H 3 - (b e n z e n e a z o b e n z e n e )-1 : 3- d ih y d r o - p h t h a la z in e - l - s u lp h o n a t e A - a c e ta t e (also -f-24EtOH) (yield 19-3%) ( B a salt, + 7 H ,0 and anhyd.). This in boiling H 20 with gradual addition of HC1 gives 1 - h y d r o x y- 3 -(b e n z e n e a z o b e n z e n e )-1 : 3- d i h y d r o p h i h a l - a z in e - d - a c e tic a c id , m. p. 177° (yield 64-2%) ( M e
ester, m. p. 153°; E t ester, m. p. 142— 143°; A c
derivative, m. p. 229°; a n i l id e , m. p. 250°), isolated through the Na salt, and reduced by SnCl2 in HC1 to l-hydroxy-3-(4' - aminophenyl) -tctrahydrophthal - azine-4-acetic acid (A., 1926, 625) and N H 2Ph.
Reduction with Na2S20 4 gives N H 2Ph. With hot H 2S 0 4 4'-amino-3-phenyl-4-methylphthalazone (A., 1931, 835) is obtained. The following are similarly obtained from 4'-nitroazobenzene-4-diazosulphate:
N a I I 3 -(4 :'-n itr o b e n z e n e a z o b e n z e n e )-l : 3 -d ih y d r o p h th /il- a z i n e - l - s u l p h o n a t e - i - a c e t a te (also + HEtOH) (yield 63-4%); l-h y d r o x y - 3 -( 4 : '- n itr o b e n z e n e a z o b e n z e n e ) - l : 3-
d ih y d r o p h th a la z in e - 4 - a c e tic a c id , m. p. 222—223°
[ A c derivative, m. p. 197° (decomp.); a n i l id e , m. p.
2S1° (decomp.)]; l-hydroxy-3-(4'-aminophenyI)tetra- hydrophthalazine-4-acetic acid (by reduction with Na2S20 4, together with a little p-phenylenediamine) (yield 51-9%); and 4'-amino-3-phenyl-4-methyl - phthalaz-l-one (and p-nitroaniline). A. A. L.
Quinazolines. III. Interaction of aniline w ith 2-chloro-4-alkoxyquinazolines and 2- chloro-4-ketodihydroquinazoline. N. A. L a n g e
and F. E. S h e i b l e y (J. Amer. Chem. Soc., 1932, 54, 1994— 199S; cf. A., 1931,1431).—2-Chloro-4-methoxy- quinazoline and EtO H -NH 2Ph give the h y d r o c h lo r id e
(I), m. p. 158—161° (decomp.), of 2 - a n ilin o A - m e th o x y - q u in a z o lin e , m. p. 113° (c h lo r o p la lin a le , softens and decomp. 225—230°; p i c r a te , m. p. 210°). Hydrolysis of (I) with dil. HC1 in EtO H -NH 2Ph gives 2-anilino-4-ketodihydroquinazoline (II), m. p. 261°, also prepared from the corresponding 2-Cl-compound and EtOH-NH2Ph, from phenyl-^-methylthiocarbamide and anthranilic acid, and when (I) is heated. 2-
A n ilin o A - e th o x y q u in a z o lin e , m. p. 110—111° [ p i c r a te ,
m. p. 183°; h y d r o c h lo r id e , m. p. 168—171° (decomp.)], is also hydrolysed to (II). These results confirm the orientation of the halogen and alkoxy-groups in the chloro-alkoxy-derivatives previously described. AH
m. p. are corr. C. J. W. (b)
Stereochem istry of dipyridyls. Preparation and resolution of 6 : 6'-diphenyl-3 : 3'-dipyridyl-2 : 4 : 3'-dipyridyl-2 ': 4'-tetracarboxylic acid. XX. E. H.
WooDRton? and R. Ad a m s (J. Amer. Chem. Soc., 1932, 54, 1977—1982; cf. A., 1931, 1295, 1306).—
The Schiff base from p-C6H4(NH2)2 (1 mol.) and PhCHO (2 mols.) with pyruvic acid in boiling EtOH gives 42—50% of 3 : 8 - d i p h e n y lA : 7-p h e n a n th r o lin e -
1 :1 0 -d ic a r b o x y lic a c id , m . p. 250-5—251-5° (decomp.)
( A g salt), oxidised by alkaline KM n04 at 20—25°
to 6 : 6'- d ip h e n y l- 3 : 3'- d i p y r i d y l - 2 : 4 : 2' : 4'-te tr a c a r b -
o x y lic a c id (I), decomp. without melting at 181°.
756 B R IT IS H C H E M IC A L A B S T R A C T S .— A .
(I) is resolved by brucine into active forms, [a]D + 6-1° and —5-9° in EtOH (b r u c in e salts), which are readily racemised by -warming with EtOH.
C. J. W. (6) Substituted piperazines. III. Stereoiso-
C. J. W. (6) Substituted piperazines. III. Stereoiso-