trihydroxy-3 : 3 ': 3 "-triniethoxytriphenylmethane, m.p.
128— 130°, and (I) and (II) give hexdhydroxytriphenyl- methane, decomp, about 250°. N. H . H.
P u rificatio n of a lco h o ls [p-phenylethyl alcoh ol].
K . H . Kl ip s t e in, Assr. to Calco Ch e m. Co., In c. (U.S.P. 2,068,415, 19.1.37. Appl., 18.5.35).—
Ph-[CH2]2-OH (I) is purified by forming a stable high-boiling ester w ith H sB 0 3, o-C6H4(C02H ) 2, (CH2*C02H )2, H2C20 4, maleic or fum aric acid, rem ov
ing im purities b y vac. distillation, hydrolysing the ester, and recovering th e alcohol. Triphenylethyl borate, b.p. 215°/1 mm ., is prepared from crude (I) w ith H3BO3 or an ester such as Bu3B 03 in presence of C6H g etc., H 20 is removed by azeotropic distillation, and the product is distilled in a current of dry air or N 2; th e borate is hydrolysed w ith h o t H 20 and (I) is separated and vac.-distilled. R . G.
M anufacture of b en zen ecarb o xylic acid flu or
id e s co n ta in in g triflu o ro m eth y l g ro u p s. W . W.
G r o v e s . From I. G. F a r b e n in d . A.-G. (B.P. 480,105, 12.8.36).—I I F or SbF3 is allowed to act on a derivative of BzCl which contains a t least one CC13 and m ay contain other substituents; th e Cl is replaced by F.
I n examples, m-, b.p. 156°/15 mm ., an d p -trichloro- methylbenzoyl chloride, b.p. 159—160°/18 mm ., afford m-, b.p. 159—162°, and p-trifluoromethylhenzoyl fluoride, b.p. 158—162°, th e former by heating with SbF3 a t 180—200° under a rectifying column and the la tte r by heating in an F e pressure vessel a t 100—
150° for 2—3 hr. and rectifying tho product. Similarly tlicro are obtained 3 : 5-bislrifluoromethylbenzoyl fluoride, b.p. 158—162°, i-trifluoromethyl-l : 2- and
5-trifluoromethylbenzene-l : 3-dicarboxyl fluoride, b.p.
88°/15 mm. K . H . S.
P ro d u ction of b en zoylb en zoic acid co m p ou n d s. I. G u b e lm a n n a n d J . M. T i n k e r , Assrs.
to E. L D u P o n t d e N e m o u r s & Co. (U.S.P. 2,068,321, 19.1.37. Appl., 27.6.35).—4'-Halogeno-3'-amino-2- benzoylbenzoic acids and th eir halogen-substitution products w ith halogen in a t least one of positions 3, 4, 5, and 6 are diazotised and tho diazo compounds trea ted w ith an alkali cyanide and a Cu salt to give th e corresponding 4'-halogeno-3'-cyano-2-benzoyl- benzoic acids which on hydrolysis w ith alkali (NaOH) give 4'-halogeno-3'-carboxy-2-benzoylbenzoic acids.
4 '-Ghloro-3'-cijano-2-benzoylbenzoic acid, m .p. 193-2°,
is claimed. R . G.
M anufacture of acyl p e r o x id e s. W. W. G r o v e s . From I. G. F a r b e n in d . A.-G. (B.P. 479,912, 12.8.36).
—Diaroyl peroxides (Bz20 2) are prepared by the interaction of an acid chloride w ith H202 or a m etal peroxide in presence of a H20-sol., in ert org. dispersing agent. The peroxides m ay be diluted during or after prep, w ith an anhyd. com pound which unites w ith H 20 to yield a fine homogeneous product. The prep, of Bz20 2 and 3 :3'-dichlorobenzoyl peroxide in presence of olevlm ethyltauride, oleyl alcohol-(CH2)20 , N a salts of sulphonic acids, and also w ith C aH P 0 4, CaC03, NaCl, or NaOAc is described. A. H . C.
P ro d u ction of d eriv a tiv es of cy c lic p-keto- ca rb o x y lic a cid s. K . Z i e g l e r , Assr. to S c h e r i n g - K a h lb a u m A.-G. (U .S .P . 2,068,284, 19.1.37. Appl.,
16.11.34. Ger., 18.11.33).— Cyclic p-cyano-ketones
and -ketimines are produced by th e interaction in solution of an arom atic ctu-dinitrile an d an alkali (Na, Li, Mg, Al) derivative of an alkylarylam ine by adding th e form er very gradually to th e latter in solu
tio n in a solvent which is preferably nearly saturated.
Exam ples are : 1 : 13-dicyanotridecane (21) added to NMoPhNa in boiling E t 20 (1-3 1.) [from NHPhM e (116), N a (20), and C1 0H8 (56 pts.)] during 72 hr. gives a-cyanotetradecanone-$-imide, m .p. 147— 148°, which by boiling w ith 70% HjSO,} gives q/ctotetradecanone, m .p. 53°. Similarly, from 1 : 15-dicyanopentadecane a n d ' azelaodinitrile are obtained respectively cyclo- hexadecanone (77% yield) and liexan-p-oneimide,
m .p. 106—107°. N. H . H.
[P rep aration of] ( a ) h a log en oa m in oflav an th r- on es and (B) com p ou n d s of th e an th raq uin one s e r ie s. W . D e t t w y l e r , Assr. to E . I. D u P o n t d e N e m o u r s & Co. (U.S.P. 2,068,312—3, 19.1.37.
Appl., 24.5.33).—Dihalogenotetra-acylamino-1 : l'-d i- anthraquinonyls are prepared b y heating an aa- dilialogeno-pp-diacylaminoanthraquinone, e.g., 1 : 5- or 1 : 8-dichloro-2 : 6- or -2 : 7-dibenzam idoanthra- quinone, w ith Cu (in boiling P h N 02 w ith N a2C 03) to give the corresponding dianthraquinonyl, e.g., 5 : 5'- dichloro-2 : 6 : 2' : G'-tetrabenzamido-l : 1 '-dianthra
quinonyl, which (a) by sim ultaneous hydrolysis and ring-closure give (in H2S 04 a t 85—90° for 4 hr.) the flavanthrone, e.g., 5 : 5'-dichloro-G : 6' -diaminoflavan- throne. The la tte r can bo converted into th e corre
sponding thiazoles b y know n m ethods. N . H . H . P rep aration of d iam in o d ip h en o xy an th raq u in - on ed isu lp h o n ic a cid s. E . C. B u x b a u m , Assr. to E . I. D u Pont d e Nem o urs & Co. (U.S.P. 2,068,373, 19.1.37. Appl., 20.5.36).— 1 : 4-Diamino-2 : 3-di- phenoxyanthraquinonedisulphonic acid or its derivatives, prepared by sulphonating, e.g., 1 :4 - diam ino- 2 : 3-diphenoxyanthraquinone (I), are isolated in th e form of cryst. sulphates by diluting th e re
action m ixture w ith H 20 to a concn. of 45— 65%
H2S 0 4. Exam ples are th e isolation from 100%
H ,S 04 of th e sulphonation product of (I) and th e corresponding di-(p-m ethylphenoxy)-derivative by pouring th e reaction m ixture into sufficient H 20 to
give 50% H2S 0 4. N . II. H .
In trod u ction of a ry l g ro u p s in to aS-unsaturated carb on yl co m p ou n d s and th e ir d eriv a tiv es.
S c h e r i n g - K a h lb a u m A.-G. (B.P. 480,617, 5.9.36.
Ger., 17.9.35).—A ryl groups are introduced (by elim ination of an a-H) into ap-unsaturated non- quinonoid carbonyl compounds (excluding compounds containing 2 CO and 2 double linkings in one cyclo- hexane ring) by trea tm e n t (in presence of Cu or Cu salts) w ith arom atic diazonium salts or their equivs. (containing negative groups) in, e.g., AcOH, E t 0 H - H20 , C0Me2- H20 , or non-H20-miscibIe solvents (CH2C12). E.g., 2?-NH2‘C6H4,N0 2 (6-9) ->
coumarin (7-3 pts.) in aq. COMe2 w ith CuS04 (0-5 pt.) a t 19° gives Z-^-nitrophenylcoumarin, m .p. 264°.
Similarly, p-CGH4Cl-NH2 (I) -> CHPh:CH-C02H, (I)->
CMe2:CHPh, (I) CHPluCH-CHO, and (1) -> cou
m arin give respectively p -chloro-, m .p. 127-5— 128-5°, and -p-chloro-a-acetyl-stilbene, m .p. 105— 106°, a-p- chlorophenylcinnamaldehyde, m .p. 125— 126°, and 3- p -chlorophenylcoumarin, m .p. 187— 188°, and
p-Cl. IV.—DYESTUFFS. 489 C jo H /N B i; ^-N H 2-CgH 4-C02H , and p-
N H 2'C 6H 4*S03H -> coum arin give respectively 3-(3- naphthylcoumarin, Z-phenylcowmarin-4-carboxylic and
-sulphonic acids. . N. H . H .
P ro d u ction of p h otograp h ic se n s itis in g c o m p ou n d s. M. Ba r e n t an d J . D. Ke n d a l l (B.P.
477,983, 6.4.36).—The compounds used as sensitisers in B .P. 456,362 ( B . , 1937, 395) are prepared by con
densing a quinoline base having reactive a- or y-Me w ith a quaternary salt of a heterocyclic base having a reactive a-thio- or -seleno-ether or -thione, -selenone, -amino-, or substitu ted amino-group in presence of a n acid-binding agent. E.g., 1-m ethylthiolbenzthia- zole m etho-jj-toluenesulphonate (I) is heated a t tho b.p. w ith quinaldine (II) in C5H 5N to give 2-methyl- dihydrobenzthiazolylidenequinaldine, m .p. 161— 162°
(also obtained from the corresponding 1-methylseleno- com pound); sim ilar compounds are formed from (I) and lepidine, m.p. 260°, 2 : 3-dimethylquinoline, m.p. 188°, 6-aminoquinaldine, m .p. 256°, 4-cthylthiolquinaldine, m .p. 185°; from 1-ethylthiolbenzthiazole etho-y>- toluenesulphonate and (II), m .p. 137°; 2-methyl- thiolquinoline m ctho-p-toluenesidphonate and (II), m .p. 153°; l-m ethylthiol-5 : 6-benzbenzthiazole (III) m etho-p-toluenesulphonatc and B-naphthoquinaldine, m.p. 305°, and (II), m.p. 226°; 1-methylthiolbenz- oxazole m etho-y-toluenesulphonate and (II), m .p.
244°; l-«-acetanilidovinylbenzthiazole m ethiodide and (II), m.p. 160°; 1 : 3 : 3-trimothyl-2-w-acetanilido- vinylindoleninium iodide and (II), m .p. 160°; 6- ethoxyquinaldine, m .p. 192°, an d ^-toluquinaldino (IV), m .p. 187°; 4 : 5-dim ethoxy-l-m ethylthiolbenz- selenazole m etho-^-toluenesulphonate and (II), m.p.
233°; 4 : 5-m ethylenedioxy-l-m ethylthiolbenzthiazole m etho-p-toluenesulphonate and (II), m .p. 235°;
4 : 5-dim ethoxy-l-m ethylthiolbenzthiazole m etho-^- toluenesulphonate and (II), m .p. 226°; 1-methyl- thiol-3 : 4-benzbenzthiazole metho-p-toluenesulphon- ate and (IV), m .p. 248°, and (II), m .p. 256°; and the etho-p-toluenesulphonate of (III) and (II), m .p. 186°.
H . A. P.
M anufacture of m e rca p to th ia zo les. W i n g f o o t C orp. (B.P. 479,855, 11.8.36. U.S., 16.10.35).—
M ercaptothiazoles (mercaptobenzthiazole) prepared by th e interaction of S, CS2, and an amine are pptd.
in a purified an d denser form b y pouring tho m olten product into clil. acid (1% aq. H ,S 0 4) a t 50—90°.
A. H. C.
M anufacture of p y rim id in e com p ou n d s. A.
C a r p m a e l. From I. G. F a r b e n in d . A.-G. (B.P.
475,507 and 475,559, 19.5.36. Cf. B .P. 473,193; B., 1938, 140).—(a) Interaction of 4-amino-5-amino- alkylpyrim idines w ith H N 0 2 gives 4-amino-5-hydroxy- alkylpyrim idines, convertible by stan d ard m ethods into esters or halides. E.g., 4-amino-2-methyl-5- am inom ethylpyrim idine hydrochloride is converted by NaNO, in I I 20 a t 50—60° into i-amino-2-methyl-5- hydroxymethylpyrimidine, m .p. 191° [-5-bromomethyl- hydrobromide, m.p. 208° (decom p.); benzenesulphonate hydrochloride']; in conc. H C l 4-amino-2-melhyl-5- chloromethylpyrimidine, m .p. 163°, is formed. Other examples describe th e prep, of 2 : 4-diamino-Q>- methyl-5-$-chloroethyl-, b.p, 163°/4 m m ., and -5-(3- acetoxyethyl-, decomp. > 200°,
4-amino-2-phenyl-5-hydroxymethyl- (hydrochloride, m .p. 199°; picrate, m .p. 177°) and -5-bromomethyl- (hydrobromide, m .p.
165°), 4-methylamino-2-methyl-5-hydroxymethyl-, m .p.
160°, and -5-cliloroviethyl-pyrimidine, m .p. 200° ; E t 4-hydroxy-, m .p. 174°, and 4-chloro-2-phenylpyrimidyl-5-acetate, m .p. 77°, and 4-amino-2-phenylpyrimidyl-5-acetamide, m .p. 209°. (b) 4-Amino-2-alkyl-5-amino-alkylpyrim idines are prepared by m ethods similar to those of B.P. 473,193, using suitably su bstituted hydroxym etliylene- or carboalkoxy-acetonitriles in the place of similarly constituted acetic esters. E.g., E t , cyanosuccinate is condensed with
NH:CMe-NH2,HCl and N a in E tO H to give E t 4- amino-6-hydroxy-2-imlhyl-5-pyrimidylacetale, con
verted by P 0C l3 and reduction of th e Cl-compound (Zn-aq. EtO H ) into E t 4-amino-2-methylpyrimidyl-5- acetate, m.p. 168°; th e corresponding amide, m .p.
250°, is converted into 4-amino-2-methyl-5-amino- m ethylpyrim idine as in B .P. 473,193. The following aro also described : 4-amino-5-cyano-2-methyl-, m .p.
249° [picrate, m .p. 215° (decomp.)], -2-ethyl-, m .p.
198°, an d -2-benzyl-pyrimidine, m.p. 180°; 4-amino- G-hydroxy-, m .p. 317°, and Q-chloro-4-amino-2-methyl- 5-fi-phthalimidoethylpyrimidine ( I ) ; 4-amino-Q- hydrazino-2-mcthyl-5-$-aminocthylpyrimidine (picrate, m.p. 195—196°) [from (I) and N2H 4,H 20 ] ; E t 4- amino-Q-hydraxy-2-benzyl-, m .p. > 300°, G-chloro-4- amino-2-benzyl-, m .p. 136°, and 4-amino-2-benzyl- pyrimidyl-5-cicetate, m .p. 130°, and the dihydro
chloride, m .p. 115°, of 4-amino-2-ethyl-5-aminomethyl-
pyrimidine. II. A. P.
H yd rocarb on s. S y n th e sis of h ydrocarb on s.
H 2-co n ta in in g g a s e s [for sy n th e sis of h yd ro
ca rb on s]. C2H 2. T rea tin g h yd rocarb on s w ith C r 0 2Cl2.—See II . In ter m ed ia tes. A ra lk yl- am in o a n th ra q u in o n es. O xazin es of an th raq uin one se r ie s. P ery len e co m p o u n d s.—See IV. S u l
p honic a c id s.—See VI. H 20 2.—See V II. A lk y lo l- a m in es fr o m so a p s.—See X II . A rtificial m a te r ia ls. See X I I I . In se c tic id e s.—See X V I.
S u lp h a n ila m id e. D eriv a tiv es of a6-aliphatic d ia m in e s.—See X X .
IV .-D Y E S T U F F S .
[P ro p erties of n ew ] B en zo F a s t Copper d yes.
K . Ot te nsch lAg er (Textilber., 1938, 19, 282—283).
—Benzo F a s t Copper Yellow GGL, Blue FB L , and N avy Blue R L are recent additions to this previously- described range (B., 1935, 721) of dyes fa st to light and washing; their properties an d uses in selected com binations are described. A. J . H.
V at d yes of th e b en zan th ron e se r ie s . X IX, X X . T. M a k i and Y. N a g a i (J. Soc. Chem. Ind.
Jap a n , 1937, 40, 471—472b).—A sum m ary of work already reported (cf. A., 1937, I I , 460). R . S. C.
S y n th e sis of in d ig o tin . F. H e n e s e y (J. Soc.
Dyers an d Col., 1938, 54, 105—115).—Experim ents on the technical synthesis of indigo (I) are described.
Optim um yields of indoxyl (II) are obtained b y fusing NHPh-CH2-C02Na(K) (1 mol.) w ith N aN H 2 (< 2 mols.) and “ mixed caustic ” (approx. 3 mols. of K O H an d 3 mols. of NaOH) at 220—225° for 5 | hr.
a t < 4 0 lb./sq. in. The reaction takes place in two
490 B R IT IS H CHEMICAL AND PHYSIOLOGICAL ABSTRACTS.—B.
stages and is adversely affected by H 20 . A deficiency of N aN H 2 leads to the form ation of N H 2Ph.
Optim um yields of (I) are obtained b y oxidising a 4%
solution of (II) a t >70° w ith a regulated stream of air in presence of 1— l -5% of a m etallic oxide (e.g., MnO). Lower yields are obtained by slower oxidation due to the form ation of o-NH2,CGH 4’C 02H and by too rapid oxidation due to the form ation of compounds of the flavindine type. Suspended oxidation of the (II) m elt solution or suspended filtration of th e dye also has an adverse effect on yield. A m ethod of analysing indigotin (III) by sulphonation to indigo- carmine and titratio n until colourless with 0-05% aq.
K M n04, a sample of (I) of known (I II) content being tak en as standard, is described. S. C.
L a k e p i g m e n t s f o r r u b b e r . —See X IV . D e t e c t i n g a r t i f i c i a l c o l o u r i n g s i n f a r i n a c e o u s f o o d s . A n n a t t o i n c h e e s e .—See X IX .
See also A., I I , 134, A z o d y e s f r o m a r y l e s t e r s o f h y d r o x y n a p h t h o i c a c i d s . 153, N e w r h o d a m i n e d y e f r o m j p - c y m e n e . 159, A z i n e c o m p o u n d s d e r i v e d f r o m d i a m i n o b e n z i d i n e .
Pa t e n t s.
M a n u f a c t u r e o f a z o d y e s a n d i n t e r m e d i a t e s .
E . I. D u P o n t d e Nem ours& Co., and F . Zw il g m ey er
(B.P. 479,848, 10.8.36).—Furoylacetarylam ides aro made by interaction of furoylacetic esters and prim ary arylamines, preferably in presence of an in ert solvent (xylene) and a catalyst (C5H 5N). In examples there are described a-furoylA-chloro-, m .p. 131— 133°, -i-viethyl-, m .p. 142—144°, -4-ethoxy-, m .p. 125—126°, -2 : 5-diethoxy-, m.p. 118—120°, -5-chbro-2-methyl-, m.p. 131— 133°, -4-chloro-2 : 5-dimethyl-, m .p. 147—
149°, A-chloro-2 : 5-diethoxy-, m.p. 154— 156°, -2- melhoxy-, m .p. 10S— 109°, -2 : 5-dimethoxy-, m.p.
121— 123°, -5-chloro-2-methoxy-, m.p. 116— 117°, and A-methoxy-acetanilide and a-furoylacet-2-methoxy-l- naplithalide, m .p. 173— 175°. The substances are used to produce azo dyes on the fibre w ith diazo compounds derived from arylam ines free from groups im parting
solubility in H 20 . K . H . S.
M a n u f a c t u r e o f a z o d y e s a n d p r e p a r a t i o n s f o r t h e p r o d u c t i o n t h e r e o f . A. C a r p m a e l. From I. G. Fa r b e n in d. A.-G. (B.P. 480,169, 14.8.36).—
Diazo compounds derived from arylamines free from H 20-solubilising groups aro combined w ith amines or imines containing S 0 3H or C 0 2H and the diazo- amino-compounds thu s formed are converted, either wholly or in p art, into salts o f volatile org. bases, preferably having b.p. 30—80°. The org. salts are mixed, either dry or in solution, w ith coupling components, printed, and developed by steaming alone, the org. base being removed, whereupon the residual acidity of the CO„H dr S 0 3H is sufficient to regenerate the diazo compound and perm it coupling.
Non-volatile bases, if present, m ust be substantially
< the q u an tity necessary to neutralise the acid liberated by removal of the volatile base. The dyes can be developed sim ultaneously with v a t dyes.
Among examples (46), 1 : 4 : 2-CGH 3MeCl*NH2 (42-5) is diazotised an d ru n a t 0—5° into a solution of 1 : 2 : 5 - N H 2-CgH 3(C02H )-S03H (80) dissolved in H „0 (300) and C6H 5N (700). A fter 4—5 hr. H 20 (1000)“is added
and N H 4C1 (500 pts.), whereupon the diazoamino- compound (I) is pp td . as yellow crystals. Salts of N H 4, N H E t2, N H 2Pr°, N H 2P r'3, and N H 2B u“ are obtained from similar diazo compounds w ith other amines and imines, e.g., NHMe-CH2*C02H , taurine, proline, and piperidine:2-carboxylic acid. A printing paste is m ade b y dissolving
2 : 3-O H C l0H G-CO-NH-CGH 4Me-o (2-8) and the N H 4 salt of (I) (5) in 75% aq. N H E t2 (20 pts.) and adding to n eu tral thickening. A fter printing and steam ing a red p rin t is obtained. K . H. S.
M a n u f a c t u r e o f d i s a z o d y e s . W . W. G r o v e s . F rom I. G. F a r b e n in d . A.-G. (B.P. 480,601, 24.8.36.
Addn. to B.P. 458,370; B., 1937, 884).—An aminoazo compound (I) m ade by diazotising 1 : 3 : 5 :4 - N 0 2‘C6H 2C12-N H 2 and coupling w ith 1 : 2 : 5 - N H 2,C6H 3(0"C2H 4,OH)2 (II) is diazotised and coupled, cither in substance or on the fibre, w ith arylam ides of 2 : S-OH-CjoHg'COaH. The ZnCl2 salt of the diazo
nium chloride o f (I) m ay also be employed. The shades obtained are navy-blues and blacks which are superior in fastness to light to the dyes of B .P.
100,804, 203,032, and 214,516 (B., 1916, 8SS; 1923, 1016; 1924, 505). In stead of (II) th e di-p-hydroxy- propoxy- or -y-hydroxybutoxy-ethers m ay be used.
Iv. H. S.
M a n u f a c t u r e o f [ a z o e t c . ] d y e d e r i v a t i v e s . S o c . Chem. In d . i n B a s l e (B.P. 480,358, 17.8.36. Switz., 17.8., 1.10:, and 21.12.35).—The H 20-solubility of hydroxylated (azo) dyes is increased by acylation in presence of a teri.-amine (C5H 5N) w ith a compound which in addition to the acylating group contains a t least one salt-forming group or a group convertible into qu aternary N H 4 by com bination w ith the tert.- amine or by addition of an alkyl salt, e.g., poly
carboxyl or -sulphonjd halides, sulphocarboxyl halides, dialkylam ino- and lialogenoalkyl-benzoyl halides.
E.g., the dye (I) a-C10H / N H 2 -> p-C10H /O H is heated w ith ^-C H 2C1-CgH 4,COC1 in C5H 5N to give the chloride of the corresponding ^-pyridm ium -m ethyl- benzoate, a H 20-sol. compound, readily reconverted into (I) by dil. aq. alkali. O ther examples describe the prep, of H 20-sol. products from a-C10H 7*NH2 ->
2 : 3-hydroxynaphthoic anilide (II), (I), or 4 : 4'- (•C0H 4-NH2)2 (III) -> p-C10H 7-OH and
7»-COCl-CfiH 4-SOoCl; (1), 1 : 4-N H 2-C10H G-S03I I ->
(II), ?>-NHAc-CGH 4-NEL ->
2 : 5 : 7-NHBz*Ci0H 5(OH)-SO2-NHPh, 1 -2 ': 4'- dinltrophenylanuno-S-hydroxynaphthalene, 1 : 5- diamino-4 : 8-dihydroxyanthraquinone and
m-C02H ,CGH 4,S 0 2C l; (I), (III), the Cu derivative of 4 : 2 : 1-NH2-C6H 3C1-0H -> p-C10H 7-OH, or 16 : 17- dihydroxydibenzanthrone and
1 : 3 : 5-CO,H-C0H 3(SO2C l),; (I) and
2 : 1 : 5 -0 H-CgH 3(C02H )-S63H, and 1 : 5-dibenz- amido-4 : 8-dihydxoxyanthraquinone and p-chloro- m ethylbenzoyl chloride. The colour in H 20 of numerous other similarly solubilised derivatives of hydroxyazo dyes is given. H . A. P.
P r e p a r a t i o n o f a r a l k y l a m i n o a n t h r a q u i n o n e s .
E. C. Bu x b a u m, Assr. to E . I. D u Pont d e Nem ours
& Co. (U.S.P. 2,068,371—2, 19.1.37. Appl., 25.3.36).
— (a) Aralkylam inoanthraquinones useful for colour
ing acetate rayon and gasoline are obtained by
Cl. IV.—DYESTU FFS. 491
heating a t 100—200°, if desired in presence of inert org. so lv e n ts' (P h N 0 2, o-CfiH 4Cl2) and a catalyst (Na2C 03), a m ixture of an aralkyl alcohol(CH 2Ph-OH) and an amino- or nitro-anthraquinone. Exam ples a r e : 1 : 8-diamino-, 1 : 4 : 5 : 8-tetra-am ino-, and 2-bromo- l-am ino-4-toluidino-anthraquinone w ith excess of CHoPh-OH a t about 200° give 1 : 8-di(benzylamino)- (violet), 4 : 8-diamino-I : 5-dibenzylamino- (greenish- blue), and 2-bromo-4:-toluidino-l-benzylamino-anthra- qiiinone (greenish-blue), respectively. Similarly, from the appropriate anthraquinone derivatives,
1 : 8-dibenzylaminoA : 5-diliydroxy-, -4 : 5-dimethoxy-, and 8-amino-\-benzylamino-A. : 5-dihydroxy-anthra- quinone are obtained. F rom 1-nitro- and l-nitro-2- m ethyl-anthraquinone are likewise obtained 1-benzyl- amino- (red) and l-benzylam ino-2-m ethyl-anthra- quinone (orange). A nother example illustrates the use of Plv[CH2]2-OH in the prep, of 1 : 8-di(phenyl- ethylamino)-4 : 5-dihydroxyantkraquinonc (blue).
(b) Polyam inoanthraquinones containing 3 a-N H , are caused to in teract w ith aralkyl halides, sulphates, or alcohols a t 100—200° in presence of alkalis so th a t a t least one N H 2 is substituted. Exam ples are : 1 : 4 : 5 : 8-tetra-am inoanthraquinone (I) (100) w ith CH2P1iC1 (300) and N a2C 03 (80 pts.) a t 140— 145° for 4 hr., or a t 175° for 4 hr. give respectively 1 : 4 : 5 : 8- tetrabenzylam ino- (II) and -tetra(dibenzylamino)- anthraquinone. Similarly, from 1-amino- and 1 :4 - aiam ino-anthraquinone are obtained the correspond
ing di(dibenzylamino)-derivatives. Other examples describe th e interaction of.(I) (100) w ith CH2Ph-OH (400 pts.) a t 200° for 4 hr. to give 4 : 8-diamino-l : 5- di(dibenzylamino)anthraquinone (III) and of (I) in P1iN02 w ith CH2PhCl (in slight excess over theory) a t 170— 180° for 6 hr. to give 4 : 5 : 8-lriamino-l- benzylaminoanthraquinone (IV). In th e interaction of (I) in P hO H w ith CH2PhCl, by the regulation of the am ount of the latter, the form ation of (II), (III), or (IV) can be controlled. N. H. H .
M a n u f a c t u r e o f a c i d w o o l d y e s o f t h e a n t h r a q u i n o n e s e r i e s . W. W . G r o v e s . From I. G.
F a r b e n in d . A .-G . (B.P. 480,270, 20.8.36).—The chlorination or brom ination of l-am ino-4-arylam ino- anthraquinone-2-sulphonic acids or their alkali salts gives dyes of redder shade th a n the starting m aterials and of good fastness properties. E.g., N a l-amino-4- p-acetam idoanilinoanthraquinonc-2-sulphonate (I) is chlorinated (Cl3) in conc. H 2S 0 4 containing a little I a t 0— 10° to give a blue C i-com pound; w ith B r a t 0—5° a B r v an d a t room tem p, a i?r2-derivative is produced. The i?r2-derivative of the p -N -Me deriva
tive of (I), and the Br- and B rr derivatives of 1-amino-4-anilinoanthraquinone-2-sulphonic acid are similarly
prepared. H . A. P.
M a n u f a c t u r e o f v a t d y e s o f t h e a n t h r a q u i n o n e s e r i e s . W. W. G r o v e s . From I. G. F a r b e n in d . A.-G. (B.P. 480,749, 26.8.36).—The use of trifluoro- methylbenzoyl halides (fluorides) as acylating agents for am inoanthraquinones and cyclic derivatives is claimed. Exam ples of the dyes produced are : 1 : 5- , m .p. 363°, 1 :8 -, m .p. 292° (both yellow), and 1 :4 - bis-p-trifiuoromethylbenzamido- (scarlet), m .p. 352—
353°, l-benzamido-5-'p-trifluoromethylbenzamido- (yel
lo w ) , m.p. 297—298°, 1 : o-dihydroxy-A : S-bis-p-tri- MM (b .)
fiuoromethylbenzamido- (violet), m.p. 349°, 1 : 5-, m.p.
290—292°, 1 :8 -, m .p. 218° (both yellow), and 1 :4 - bis-m.-trifluoromethylbenzatnido-, m .p. 212° (red), 1- benzamido-5-m-trifluoromethylbenzamido- (yellow), m.p.
250°, 1 : 5-dihydroxyA : 8-bis-m-trifluoromethylbenz-amido- (violet), m .p. 320°, and 1 : 5-bis-o-trifluoro- methylbenzdmidoanthraquinone (yellow), m .p. 311°;
4-n\-trifluorom.ethylbenzamido-2 : l-a7ithraqui?ionebenz- acridone, m .p. 284° (Cl2-fast), and its Q'-Cl-, m .p.
318°, and 3' : 5 '-Clv derivative, m .p. 291° (all blue), and -!($) : 2-thioxanthone (blue-red), m.p. 305°;
3 ': 5'-dichIoro - 4 - 3” : 5 " - bistrifluoromethylbenzamido- 2 : 1 - anthraquinonebenzacridone, m .p. 341° (blue);
4 - p - Irifluoromethylbenzamido - 1 : 9 - anthrapyrimidine (green-yellowr), m .p. 220°, and -2 : 1-anthraquinone- bcnzacridone (G'-Ci-derivative, m .p. 393°).
H . A. P.
M a n u f a c t u r e o f v a t d y e s o f t h e d i b e n z a n t h r o n e s e r i e s . G. W. J o h n s o n . From I. G. F a r b e n i n d . A.-G. (B.P. 480,284, 22.8.36).—Blue-green to blue v at dyes are obtained by interaction of aroyl halides with dihydroxy-di- or -wodi-benzanthrones, their alkyl ethers, or acyl esters, or w ith a dibenzanthrone-16 : 17- quinonc in presence of F e or F e h alid es; one or more aroyl groups are introduced, ap parently directly into the nucleus, and the compounds having > 2 of such are in general v a ttc d w ith difficulty. E.g., (16 : 17-) dihydroxydibenzanthrone (I) is heated -with BzCl and Fe in C6H 3C13 a t the b.p. for 48 h r . ; a green-blue v at dye is produced. Similar products are obtained from (I) and 2 : 4 : 1-C6H 3C12*C0C1 (II), 1-chloroanthra- quinone-2-carbonyl chloride, from the Me2 ether of (I) and BzCl, from the bis-2' : 4'-dichlorobenzoate of (I) (with FeClj), and from dihydroxy/sodibenzanthrone
and (II). H . A. P.
P r e p a r a t i o n o f d y e s o f t h e a n t h r a q u i n o n e s e r i e s . [ B r o m i n a t e d d i m e t h o x y d i b e n z a n t h r - o n e s . ] W. L. R i n t e l m a n and W. H . L y c a n , Assrs. to E. I. D u P o n t d e N e m o u r s & Co. (U.S.P.
2,068,350, 19.1.37. Appl., 23.10.35).—In the brom ination of dim ethoxydibenzanthrones in conc.
H 2S 0 4 dem ethylation is avoided by adding (a) to the H 2S 0 4 before dilution or (b) to the H 20 used for dilution substances capable of removing free Br, e.g., (a) PhO H , cycZohexanol, quinol, (b) N a H S 0 3.
H . A. P.
[ P r e p a r a t i o n o f ] a n t h r a q u i n o n e [ v a t ] d y e s .
R. J . L o v e lu c k , and I m p e r ia l Chem. I n d u s t r i e s , L t d . (B.P. 480,745, 24.8.36).—Tribenzam idotri-anthrim idecarbazoles, prepared by interaction of a 4 : 5-dihalogeno-l-bcnzam idoanthraquinone w ith 1- amino-4- (I) or -5-benzamidoanthraquinone (II) (in P h N 0 2 in presence of a Cu salt and an acid-binding agent) and cyclisation (H2S 0 4, A1C13) followed by oxidation (NaOCl, C r03) are dark brown v a t dyes of good fastness to light, chemick, washing, and kier- boiling. The triatilhrimides and carbazoles from 4 : 5-dichloro-l-benzam idoanthraquinone and (I) or (II) (2 mols.) or (I) plus (II) (equimols.) are
described. H . A. P .
M a n u f a c t u r e o f o x a z i n e s o f t h e a n t h r a q u i n o n e s e r i e s . W. W. G r o v e s . F rom I. G. F a r b e n in d . A.-G. (B .P . 480,693, 25.8.36).—1-Halogenoanthra- quinone-2-sulphonic acids are caused to in teract w ith
492 B R IT IS H CHEMICAL AND PHYSIOLOGICAL ABSTRACTS.—B.
an o-hydroxyamino-compound in presence of an acid- binding agent (and Cu or a Cu com pound); the products are optionally sulphonated to give wool dyes.
E.g., K l-iodoanthraquinone-2-sulphonate (I) is heated a t 50—55° w ith o-OH*C6H 4-NH2, NaOH, N a2C 03, and CuCl in H 20 under N 2 to give anthra- quinone-2 : 1-oxazine; th is is converted by 8% oleum a t 25° into a blue wool dye. O ther examples describe the prep, of oxazines and their sulphonic acids (where n o t already sulphonated) from (I) and
1 : 2 : 3 : 5 : 6 : 4 - 0H -C fiCl3(NH2)-S03H (blue-red), 1 : 3 : 4 : 5 : 6 : 2-OH,CsCl4,N H 2 "(II) (not su lp h o n ated : blue-red v a t dye), 1 : 6 : 2 : 4-0H*C6H 2Cl(NH2)*S03H (red-violet), 4 : 1 : 3 : 5-0H*C6H 2Me(NH^)*S03H (violet), 1 : 2 : 4 : 6 - 0H -C GH 2(NH2)(NHAc)-S03H (I II) (violet), 3-amino-4-hydroxybenzophenone-2'- carboxylic acid [cyclised w ithout sulphonation by H „S04 a t 90—100° to a violet v a t d y e ; a sim ilar dye is obtained from (I) or the corresponding Br-com pound and l-am ino-2-hydroxyanthraquinone], 3-amino-4- hydroxydiphenylsulphone-3'-sulphonate (red-violet), and 2-amino -1 - naphthol - 4 - sulphonate (blue-grey);
from l-iodo-4-anilinoanthraquinone-2-sulphonic acid and ( I I ) ; from N a 1 - brom oanthraquinone - 2 - sulphonate and 1 :2 :4 : 6 - 0H -C 6I I 2(NH2)(N 02)-S03H (red - v io let); from l-iodoanthraquinone-2 : 6-disul- phonic acid and 5 : 2 : 4 : 1-NH2-C6H 2(0 H )2-C02H (blue; green after chrom ing); from N a 4-brom o-l- iodoanthraquinone-2-sulphonate and (I II) (violet);
and from N a 4 - bromo -1 - aminoanthraquinone-3- sulplionate w ith o-OH-CBH 4‘N H 2 (violet).
H. A. P.
M a n u fa c tu re of v a t d y es of th e a n th ra q u in o n e ox az o le s e r ie s . G. W. Jo h n s o n. Erom I. G.
Fa r b e n i n d. A.-G. (B.P. 478,700, 20.7.36).—V at dyes of good fastness to light, Cl2, and kier-boiling are obtained by condensation of anthraquinone- oxazoles derived from a non-vattable arom atic acid having reactive halogen or N 0 2 w ith cyclic prim ary or sec. amines, by condensation of oxazolcs of th e above ty pe b u t having N H or N H 2 as substituent w ith cyclic acylating agents or w ith cyclic carboxylamides in presence of acid catalysts, or by interaction of cyclic compounds attached by N H or CO'NH to a non- vattable arom atic carboxylic acid, amide, or halide, or aldehyde or di- or tri-halogenom ethyl compound with o-halogeno- or hydroxy-am inoanthraquinones.
E.g., (x-jj-aminophenylanthraquinone-1 [N) : 2-oxazole (from l-am ino-2-hydroxyanthraquinone and p- N 0 2-C6H 4-C0C1, followed by reduction w ith N a2S20 4) is heated a t th e b.p. w ith anthraquinone-2-carboxyl chloride until HCI is no longer evolved, to give a green-yellow v a t d y e ; similar dyes are obtained using 1 : 4-dichloroanthraquinone-6- (I), 1-amino- anthraquinone-2- (II), anthraquinone-2(<S) : 1-thio- xanthone-6'-, benzanthrone-6-, 1(AT) : 2-pyrazoloan- thraquinone-Py3- (from l-am ino-2-ethylanthraquinone and HNOa, followed by oxidation) and its N -Me derivative (oxidation of l-chloro-2-^-tolylanthra- quinonetol-chloro-2-;p-carboxybenzoylanthraquinone, and trea tm e n t w ith N2H 4,H20 ), an d anthraquinone-1 (N) : 2 : anthraquinone-1 ': 2'-benzacridone-5'-carboxyl chloride (III), and BzOH or N H 2Bz and HCI; n-p-amino- phenylanthraquinone-2 : 3-oxazole and (I), (II), (III), and l-nitroanthraquinone-2-carboxyl chloride;
\x-p-chlorophenylanthraquinone-l(iV) : 2-oxazole and 1- am ino-5-benzam idoanthraquinone (IV) [heated with NaOAc and Cu(OAc)2 in P h N 0 2], l-am ino-4-benz- am idoanthraquinone (V), or 5-am ino-l : 9-anthra- py rim idin e; (/.-m-nitrophenylanthraquinone-l(jV) : 2- oxazole and 1-am inoanthraquinone (VI) or (IV );
[i-2' : 4'-dichlorophenylanthraquinone-l(iV) : 2-oxazole [from l-am ino-2-hydroxyanthraquinone (VII) and 2 : 4 : l-C fiH 3Cl2-C02H in P h N 0 2] or th e correspond
ing 3 : 4-Cl2-compound and (IV), (V), or (V I); (VII) and 2>-l-anthraquinonylaminobenzoyi chloride (from 1-chloroanthraquinone an d £>-NH2-CcH 4-C02H, followed by SOC1,), j)-2-anthraquinonylcarbam ido- benzoyl chloride, or th e chloride of 1-m-carboxy-
benzam idoanthraquinone. H . A. P.
M a n u fa c tu re of [c h ro m e ] d y es of th e t r i a r y l - m e th a n e s e r ie s . W. W. G rov es. From I. G.
Fa r b e n i n d. A.-G. (B.P. 480,328, 18.8.36. Addn.
to B .P. 472,757; B., 1938, 142).—Very fast dyes of th e triarylm ethane series, capable of being chromed,
to B .P. 472,757; B., 1938, 142).—Very fast dyes of th e triarylm ethane series, capable of being chromed,