C h lo rin a te d s o lv e n ts . J. D. Co n v e r s e (Canad.
Chem., 1938, 22, 361—364).—A brief review of m anufacture, stabilisation, toxicity, and applications.
C o n d u c to m e tric a n a ly s is of m ix e d s u lp h u ric a n d b u ty ls u lp h u r ic a c id s . M. A. Ch o o h l o v k i n
and A. V. Ka l a t s o h e v a (Sintet. K autschuk, 1936, No. 3, 8—9).—The curve shows a slight break when all free H 2S 0 4 is titrated and only B uH S 04 remains.
OTN-Ba(OH)2 is used. Ch. Abs. (e) S y n th e s is of fa tty a c id s b y o x id a tio n of h y d ro c a rb o n s . G. Wi e t z e l (Angcw. Chem., 1938, 51, 531—537).—A lecture.
P r e p a r a tio n of o x alic a c id f r o m s a w d u s t.
B. I. Le o n o v (Prom. Org. Chim., 1938, 5, 489—
492).—H 2G20 4 is obtained in 40—50% yield by heating 1 : 1 m ixtures of Ca(OH)2 and sawdust a t 200°/10 atm ., for 1-5 hr. R. T.
A p p lic a tio n s of fo rm a ld e h y d e . I I . I n th e i n d u s tr ia l field . A. Mo n t e g a z z a (M at. P la s t., 1938, 5, 9—12; cf. B., 1937, 212).—A review.
D e te rm in a tio n of s o d iu m fo rm a ld e h y d e s u lp h - o x y la te a n d fo r m a ld e h y d e -s o d iu m b is u lp h ite in p re s e n c e of e a c h o th e r. L. Sp i t z e r (Annali Chim.
Appl., 1938, 28, 252—254).—W ith m ixtures of the two compounds, I '- I 0 3' and NaOH are added, followed, after 15 min., by HC1; I is th en titra te d with 0-lN-Na2S20 3. A further sample is treated w ith excess of lfgCl2, which is oxidised to HgCl only by CH20 -N a H S 0 3; the HgCl is separated and deter
mined iodometrically. The difference in I titres gives th e equiv. of sulphoxylate. F. O. H .
Im p ro v e d te c h n iq u e fo r p r e p a r in g m -n itro a n il- in e fro m m -d in itro b e n z e n e . E. A. Ca l d e r6n
(Anal. Asoc. Qufm. Argentina, 1938, 26, 30—32).—
25% ?m-C6H 4(N 02)2 in boiling H 20 w ith a boiling solution containing 23% of N a2S,9H20 and 6% of S gives 60-87% of m -N 02-CGH 4-NH2. “ F. R. G.
A n a ly sis of te c h n ic a l p -n a p h th y la m in e - l- s u l- p h o n ic a c id . K. D. Sc h t s c h e r b a t s c h e v (Prom.
Org. Chim., 1938, 5, 4 2 7 -^ 2 9 ).—7 g. of the product are dissolved in 100 c.c. of H 20 a t 80°, th e solution is m ade alkaline with aq. N H , and filtered, and th e filtrate + washings are diluted to 250 c.c. 25 c.c.
of solution are titra te d with 0-lN-NaN02 (A c.c., = the sum of 1-, 6-, and 8-sulphonic acids). 1 c.c. of conc. HC1 is added to a second 25-c.c. portion of the solution, which is filtered after 30 m in .; th e S 0 4"
content of the filtrate + washings is determ ined by adding 25 c.c. of 0-2M-BaCl2, excess of which is titra te d with 0-05M-K2Cr20 7 (B c.c.). 25 c.c. of 40% NaOAc are added to a third 25-c.c. portion of solution, and AcOH is added to give a faintly acid reaction, followed by 25 c.c. of 0-2N-diazobenzene-2 : 5-disulphonic acid. 0-2N-diazobenzene-20 c.c. of 7% aq. N H 3 are added after 90 min., and S 0 4" is titra te d as before [C c.c. of 0-05m-K2Ct20 7). The % content of [3- naphthylam ine-l-sulphonic acid is given by 100(1 —
A + 0 - B )/A . R. T.
C o n d e n sa tio n of m ix e d v a p o u r s .—See I. S te e ls in m a n u fa c tu re of o rg . a c id s .—See X. N a p h th e n
-C l. I I I . —ORGANIC IN T ERM ED IA TES. 1133 a te d r ie r s .—See X III. S y n th e tic ta n n in g a g e n ts .
—See XV. E tO H fr o m p o ta to e s .—See X V III.
D e te rm in in g s a c c h a rin .—See X IX .
See also A., I, 465, A nodic o x id a tio n of a c id - e s t e r s a lts . II , 345, S y n th e s is of «~C7H 16. 346, C a ta ly tic p r e p , of j’s o a m y l a c e ta te . 347, E le c tro ly tic p r e p , of C a g lu c o n a te a n d o th e r s a lts of ald o n ic a c id s. 354, P r e p , of c u m u le n e s . 376, E le c tro ly tic re d u c tio n of g lu ta rim id e a n d its d e r iv a tiv e s . 377, S y n th e se s of p y rr o le a n d indole d e riv a tiv e s . P r e p , o fis a tin -fi-o x im e . 379, P re p , of h is tid in e . 386, D e te rm in in g M e B r in a ir , E tO A c , a n d of C 5H 5N .
Pa t e n t s.
C h lo rin a tio n of m e th a n e o r a h o m o lo g u e th e re o f. I . G. Fa r b e n i n d. A.-G. (B.P. 489,553, 29.1.37. Ger., 28.1.36).—CH4 or a lower homologue is preheated and passed with Cl2 a t high velocity through a thin porous layer or tissue of a contact m aterial. This process strongly favours th e pro
duction of Clr and Cl2-compounds. The chlorination of CH4 a t 450—480° (preheated to 250°) and of C3H 8 a t 350—370° (preheated to 220—240°) over a quartz filter is described. A. H . C.
M a n u fa c tu re of h ig h e r c h lo rin a te d m e th a n e s .
I . G. Fa r b e n i n d. A.-G. (B.P. 489,554, 28.1.37.
Ger., 29.1.36).—MeCl or CH2C12 is further chlorinated in the liquid phase and w ith exposure to light and th e resulting m ixture continuously fractionated so th a t unaltered starting m aterial is returned to the chlorination vessel A pparatus and the production of CH2C12 containing 2— 10% of CHC13 and CHC13 containing 10% of CC14 are described. A. H. C.
M a n u fa c tu re a n d a p p lic a tio n [to te x tile s ] of p o ly m e ris e d alk y len e o x id e s. Br i t. Ce l a n e s e, Lt d. (B.P. 487,652, 29.10.37. U.S., 7.11.36).—
Polyalkylene oxides, useful as sizes and lubricants for textiles, are produced by treating an alkylene oxide, particularly ethylene, propylene, tetram ethyl- ene, and isobutylene oxides, and homologues and iso- merides thereof, in liquid condition with an activated A120 3 earth at, e.g., 0° for 2 to 7 days. The earth (fuller’s earth) m ay be activated by heating a t 370—
480°. N. H. H.
M a n u fa c tu re of m o n o v in y la cety len e . Dr. A.
Wa c k e r Ges. f. e l e k t r o c h e m . In d. G.m.b.H.
(B.P. 488,815,16.7.37. Ger., 17.7.36).—CH;C-CH:CH2 is obtained by passing CZH 2, in th e gas phase, over a catalyst consisting of a Cu1 salt (CuCl), a sol. salt, preferably a halide, of another m etal of groups I — I I I including the rare earths (e.g., MgCl2), and either a polyhydric alcohol (butylene glycol, glycerol, mannitol, dulcitol) or an inorg. or an org. compound of N not derived from a N-acid (NH4C1, N H 2Ph,HCl, urea, acid amides, nitriles), a t 100— 180°. The C2H 2 m ay contain a little AcOH. S. C.
P ro d u c tio n of o x id a tio n p ro d u c ts fro m a li
p h a tic h y d ro c a rb o n s . H e n k e l & Co., G.m.b.H.
(B.P. 489,443, 26.1.37. Ger., 31.3.36).—Higher aliphatic hydrocarbons are continuously oxidised
(at a raised tem p, and in presence of a catalyst) and a portion of the product is continuously saponified
with alkali an d unsaponified m aterial returned to th e oxidising chamber. Suitable apparatus is claimed, and the oxidation of paraffins, b.p. 270—360°, a t 105—115° in presence of Mn palm itate and saponific
ation with soda is described. [Stat. ref.]
A. H . C.
M a n u fa c tu re of s u rfa c e -a c tiv e a g e n ts . G. W.
Jo h n s o n. From I. G. Fa r b e n i n d. A.-G. (B.P.
4S7,669, 20.10.36).—The products of halogenation of saturated aliphatic or cydoaliphatic hydrocarbons of < C8 are condensed with arom atic OH-compounds or their derivatives in presence of Zn d u st; th e con
densation products are optionally hydrogenated, and converted into H 20-sol. derivatives. The use of Zn in place of A1C13 as condensing agent is claimed to give colourless products. E.g., a hydrocarbon m ix
ture (I) of m ean mol. wt. 153 obtained by hydro
genation of brown coal (80% has b.p. 70— 130°/20 mm.) is chlorinated a t 95° (wt. increase 13%) and the product is heated with PhO H and Zn d u st a t 65—
90°; the condensation product is freed from u n changed (I) and ZnCl2, distilled in a vac., and con
densed with twice its wt. of (CH2)20 (II) a t 140—
160°, to give a soap substitute. Other starting m aterials exemplified are petroleum distillates (b.p.
180—290°), mixed crcsols, and OH-[CH2]2-OPh, and H 20-sol. products are obtained by condensing w ith (II) and sulphonating, condensing with cpichloro- hydrin follo\£cd by NMeg, and condensing with CH0-CH(S03H )2. [Stat. ref.] H. A. P.
P r o d u c tio n of g ly co ls. C. Ba r b i e r i (B.P.
489,576, 29.1.37).—Olefines which may contain inert diluents (saturated hydrocarbons) are injected in a fine state with Cl2 into a stream of cold H.,0 and the chlorohydrin is hydrolysed to glycerol. The chlorin
ation of cracking gas (32-3% of olefines), treatm en t of the (distilled) chlorohydrin m ixture with alkalino- earth hydroxide or carbonate [Ca(OH)2], an d hydros lysis of th e resulting olefine oxide with dil. H 2S 0 4
is described. A. H. C.
C o n c e n tra tio n of a lip h a tic a c id s. Br i t. Ce l a n e s e, Lt d. (B .P . 489,259, 9.11.37. U.S., 14.11.36).—
Aq. aliphatic acids (AcOH) free from mineral acid are conc. by extracting with EtOAc-C6H e (70—80 : 30—
20) after adding 0-05—4% of a conc. aq. solution of an alkali salt (e.g., N a2S 0 3) to inhibit hydrolysis of EtOAc. Corrosion is inhibited by coating the interior of the extraction apparatus with urea-C H 20
resin. A. H. C.
P ro d u c tio n of fa tty a c id s [by fe rm e n ta tio n ].
C. We i z m a n n (B.P. 489,170, 18.1.37).—The spent wash derived from COMe2-B uO H ferm entation of cereal (rice, maize) or sugary (molasses) m ash is further ferm ented with a similar form of bacillus a t 35—37° to yield fa tty ackls (chiefly P rC 0 2H , 34 pts. from 275 pts. of molasses) (cf. B .P. 4845 of 1915 and 164,366; B., 1919, 301; 1921, 598).
A. H. C.
M a n u fa c tu re of e s te r s of fi-a c e ty la m in o b u ty ric a c id . F. Ho f f m a n n- La Ro c h e & Co. A.-G. (B.P.
488,702, 29.3.38. Ger., 29.5.37).—Ale, b.p. 150—
151°/14 mm., m .p. 53—54°, Et, b.p. 152— 153°/14 mm., Pr°-, b.p. 164—165°/14 mm., and PrP, b.p. 155—
156°/14 m m ., $-acetamidobutyrate are obtained by
hydrogenation of the corresponding (3-acetamido- crotonates in presence of Ni, Pd, etc. S. C.
M a n u fa c tu re of h ig h e r h a lo g e n a te d k e to n e s.
I. G. Fa r b e n i n d. A.-G. (B.P. 489,552, 28.1.37.
Ger., 28.1.36).—Monohalogenated aliphatic ketones (made by injecting halogen in countercurrent to the vaporised ketone a t < the b.p. of the halogenated product) are further directly halogenated a t < the b.p. of the monohalogen compound. The bromin- ation of COMe-CH2B r to a m ixture of CO(CH2Br)2 and COMe-CHBr2 and the chlorination of
COMe-CHoCl to a m ixture of CH2C1*C0*CHC12 and
COMe-CCl3 is described. A. H. C.
C o u n te ra c tin g p o ly m e ris a tio n of m e th y l v in y l k e to n e d u r in g d is tilla tio n o r s to ra g e . W. W.
Gr o v e s. From I. G. Fa r b e n i n d. A.-G. (B.P.
489,634, 29.1.37).—Polymerisation of COMe’CH!CH2 during storage or distillation (e.g., from m ixtures with CHoiCH-C-CH) is minimised by adding a small am ount of an unsulphonated org. acid sol. in H 20 and the ketone (AcOH etc.). A. H. C.
M a n u fa c tu re of u r e a . Co m p, d e Pr o d. Ch i m.
e t El e c t r o m e t a l l. Al a i s, Fr o g e s e t Ca m a r g u e
(B.P. 488,404, 30.11.37. F r ., 9.12.36).—U re a is m an u factu red b y passing a suspension in a n inert liquid, e.g., a m ineral oil, o f N H 2-C02N H 4 prepared in a closed vessel from residu ary gaseous C 02 and liq u id N H 3, b o th d erived from a p receding operation, in to a urea-form ing au to cla v e a t 150—250°, togeth er w ith fresh C 02 an d N H 3. N. H. H.
M a n u fa c tu re of c o llo id a l u re a -a ld e h y d e co n d e n s a tio n p r o d u c ts . Ka l l e & Co. A.-G. (B.P.
488,686, 28.9.37. Ger., 1.10.36).—H 20-sol. colloids which are particularly valuable as additions to soaps are prepared by condensing a m ixture of H 20-sol.
interm ediate condensation product of urea or its derivatives with CH20 or (CHO)2 in presence of a H ,,0-sol. ether (I) of a highly polymeric carbohydrate (cellulose) in aq. solution while stirring. Sp. claim is m ade where 1-5—2-5 (2-0) mols. of urea are used per mol. of CH20 , and especially when (I) is a H 20- sol., preferably "highly viscous, m ethylhydroxyethyl-
cellulose. R. G.
M a n u fa c tu re of s u b s titu te d c a rb o x y lic ac id a m id e s a n d t h e i r p o ly m e ris a tio n p r o d u c ts . E. I.
D u Pont de Nemours & Co. (B.P. 489,311, 25.1.37.
U.S., 24.1.36).—The interaction of an ester of an a-methylenemonocarboxylic acid (I), e.g.,
CH2;CMe,C 02Me (II), w ith an alkali-metal derivative of a carboxylamide, e.g., N H 2-CO-NHNa, preferably in presence of a catalyst (COMe2, Bu°OH) and, if desired, a solvent (excess of the catalyst, or a hydro
carbon), at, e.g., —40° to 200° under pressure gives substituted carboxylamides in which a t least one H attached to N is replaced by the acyl group of (I). The products are polymerised by known methods, either alone or with other polymerisable substances, to give products useful as moulding, coating, sizing, etc. compositions. E.g., (II) (100) and HCO’N H , (45) in liquid N H 3 (623) with N a (23 pts.) for 16 hr.
a t room temp, give on diluting with H 20 , extracting the product with E t20 , and distilling monometh- acrylylformamide. Methacrylyl-urea and -thiourea
are formed similarly. The polymerisation of these products, both alone and with, e.g., (II), is described.
N. H. H.
M a n u fa c tu re of n i tr ile s . R . Gr e e n h a l g h, and
Im p e r i a l Ch e m. In d u s t r i e s, Lt d. (B.P. 488,036, 29.12.36).—C0C12 is heated with monobasic aliphatic saturated or olefinic amides ( < C8) either alone or in a solvent (e.g., xylene) a t 100—150°. Tho prep, of nitriles of stearic, oleic, and mixed coconut oil fa tty
acids is described. A. H. C.
P r e p a r a tio n of p o ly m e ris e d n itr ile s . Ar m o u r
& Co. (B.P. 488,808, 10.4.37. U.S., 27.7.36).—
Aliphatic acid nitriles > C 4 are polymerised by treatm ent -with catalysts such as A1C13, ZnCl2, FeCl3, SnCl4, S2C12, PC13, P 2S5, S, P, a t >100°. I n the examples, m ixtures of palmito- and stearo-nitriles, lard fa tty acid nitriles, and cracked nitriles from these products are treated with A1C13 to give thick, heavy oils suitable for use as dielectrics. S. C.
C o n d e n sa tio n of o rg a n ic m e ta l d e riv a tiv e s w ith a c y la te d c o m p o u n d s . N. V. Ch e m. Fa b r.
Se r v o, and M. D. Ro z e n b r o e k (B.P. 489,026, 14.10.36).—The interaction of esters of aliphatic carboxylic acids (I) of > C4 or of O H -fatty acids (II) acylated on the OH with carboxylic acids or their esters or alkali salts with aliphatic, arom atic, carbo- cyclic, or heterocyclic mono- or poly-hydric prim ary, sec., or tert. alkoxides or phenoxides and/or org.
m etal compounds in which th e H attached to C is replaced by m etal, e.g., m etal derivatives of E t2 malonate, gives the corresponding ether and th e m etal salt of (I) or (II). E.g., the Ac derivative of octan-(3-ol (200) with P rC 0 2N a (150 pts.) a t 125° for 2 hr.
gives a product, Ac val. 245, which probably contains an ether. The prep, of ethers from ricinoleic acid and malonic acid, terpenyl alcohol and oleyl alcohol, the E t, Bu, glyceryl, and P h ethers of ricinoleic acid,
etc. is described. N. H . H .
M a n u fa c tu re of flu o re n e d e riv a tiv e s . G . Sh e l-
d r i c k, M. Wy l e r, and Im p e r i a l Ch e m. In d u s t r i e s, Lt d. (B.P. 489,612, 27.1.37).—Interaction of fluorene, NPhEt-COCl (I), and A1C13 gives fluorene-2-carboxy- ethylanilide, m .p. 163°, and - 2 : 7 -biscarboxyethyl- anilide (best in presence of NaCl), m.p. 174—175°.
Fluorene-2-carboxylic, m.p. 278°, and -2 : 7-dicarboxylic acid are produced on hydrolysis with 65% H 2S 0 4 or K O H -E tO H . The reaction is applicable to homo-
logues of (I). H . A. P.
M a n u fa c tu re of n a p h th a le n e d e r iv a tiv e s . G. W.
Jo h n s o n. From I. G. Fa r b e n i n d. A.-G. (B.P.
489,236, 22.1.37).—A C10H 8 derivative useful as a (reddish-blue) dye for acetate rayon or as an inter
m ediate for dyes is prepared by adding (until th e p a is —9) a non-oxidising basic substance, e.g., aq.
solutions of alkali hydroxides an d carbonates or N H 4 or quaternary N H 4 bases, to solutions obtained by th e action of S sesquioxide or H 2S on 1 :5 - Cj„Hf>(N 02)2 in conc. or fuming H 2S 0 4 or C1S03H
and diluting with H 20 . N. H . H.
M a n u fa c tu re of n itr o g e n c o m p o u n d s . W. J.
T e n n a n t . From H e n k e l & Co., G.m.b.H. (B.P.
489,190, 1.3.37).—sec.- and tert.-Amines and q uatern
ary compounds are obtained by treating nuclear
alkyl-Cl. I I I . —ORGANIC IN TERM ED IA TES. 1135 (< C4) -substituted hydroarom atic amines with alkyl
ating agents, e.g., alkyl halides, sulphates, alkylene oxides, and aldehydes, preferably a t elevated temp.
The following are described : compounds from the interaction of (4-sec.-octylcycZohexyl)methylamine and glycide (at 160— 170°), and (CH2)20 (at 130— 140°);
2-methyl-4 - sec. - alkyl - (C6-10)-c)/cfohexylamines, b.p.
135—155°/2 mm., and CH2Cl-CH,-S03Na (in dil.
E tO H a t 160°); CH2C1-CH2-0 H and"C5H 5N (at 100—
110°) followed by sulphation with C1S03H , and CH2Cl-C02N a ; ^-(i-dodecylcyclohexyl)-'N-benzyl-'N- dimethylammonium methosulphate, (2-r«e<AyZ-sec.-4- dodecyloyclohexyl)viethylammo7num methosulphate, (:2-methyl-4:-sec.-clodecylcyclohexyl)dimethyla7nine, b.p.
155—160°/2 mm., and the corresponding amine oxide.
The products are used as foaming, wetting, and capillary-active agents and disinfectants. S. C.
M a n u fa c tu re of 4 -n itro -2 -a m in o -l-[h y d r]o x y - n a p h th a le n e s u lp h o n ic a c id s . Soo. Ch e m. In d. i n Basle (B.P. 487,718, 11.5.37. Switz., 14.5.36).—
The corresponding 2 : 4-dinitro-l-naphthol(-6-, -7-, or -8-)sulphonic acid is reduced by O-free S compounds of the alkaline-earth m etals. E.g., 1 : 2 : 4 : 8- 0H -C 1QH,j(N02)2-S03N a is reduced by N a2S and MgCL in H ,0 a t 40—50° H . A. P.
M a n u fa c tu re of a m in o a lk y l e s te r s of c a rb o - cyclic a c id s a n d of a lip h a tic am in o -a lc o h o ls th e re fro m . T. Sa b a l itsc h k a and E. Bohm (B.P.
487,824, 4.1.38. Ger., 22.6.37).—The estcrification of carbocyclic acids w ith alkylene diols in presence of gaseous H B r (or HC1) and treatm en t of tho resulting halogenoaLkyl esters with amines gives aminoalkyl esters of the carbocyclic acids, which are saponified to the corresponding amino-alcohols; e.g., p- 0 H 'C aH4-C02H (40) with trim ethylene glycol (50 pts.) and gaseous HC1 by warming for 8 hr. gives n-y- clxloropropyl 'p-hydroxybenzoate, m.p. 72°, which on warming with N H E t2 yields y-diethykimino-n-propyl
■p-hydroxybenzoate, m.p. 133°, the la tte r being con
verted by K O H into y-diethylamino-m-propyl alcohol, b.p. 90723 mm. Similarly, $-chloroethyl, b.p. 180°/20 ram., and $-diethylaminoethyl anisale and (J-diethyl- am inoethyl alcohol, b.p. 70°/35 mm., and $-chloro- and p-diethylaniino-isopropyl, b.p. 178°/35 mm.,
■p-hydroxybenzoate are prepared. N. H . H.
M a n u fa c tu re of d e riv a tiv e s of a-[h y d r]o x y -[2 -]
n a p h th o ic a c id . W. W. Gr o ves. From I. G.
Fa r b e n in d. A.-G. (B.P. 487,770, 22.9.36).—Halides of 1 : 2-OH*C10H 6*CO2H are condensed with colourless or slightly coloured polynuclear amines which have the property of forming substantive azo dyes. The products are used as interm ediates for th e prep, of non-diffusible azo dyes for colouring (gelatin) photo
graphic layers. Exam ples are th e bis-l-hydroxy-2- naphthoyl derivatives of benzidine, m-tolidine, 3 : 3'- dichlorobenzidine, 2 : 7-diaminocarbazole, benzidine
s ' : 3'-dicarboxylic acid, 4 : 4'-bis-p-aminobenz- amidostilbene-2 : 2'-disulphonic acid, and 4 : 4'-bis-j»- aminobenzamidodiphenyiurea-2 : 2'-disulphonic acid (“ Diazo h g h t yellow 2G ” ). H . A. P.
R eco v ery of p h e n o ls . Ba k e l it e, Lt d. (B.P.
488,574, 9.1.37. U.S., 30.6. and 24.7.36).—Phenols, e.g., m ixtures of PhOH, cresols, and xylonols, are
4h (b.)
extracted from aq. liquors by treatm en t w ith ta r acids of higher b.p. th an the phenols (b.p. <230°). After separation of the layers, which can be facilitated by adjusting the p s to < 3 (1-5—1-8), the phenols are recovered by distillation. Tars or ta r oils are sub
jected to a t least two washes with NaOH, the first with < enough to combine with all the phenols and the last with an excess; the last wash is used as th e first in subsequent stages. The N a plienolate is distilled and the distillate passed in contact w ith neutral oil (saturated with CSH SN) to absorb phenols
carried over. N. H . H.
[ P r e p a r a tio n of] c h lo rin a te d a r a lk y l k e to n e s.
[L u b ric a n ts .] Ar m o u r& Co. (B.P. 487,642,7.10.37.
U.S., 9.3.37).—Aralkyl ketones, e.g., Ph, tolyl, or xylyl heptadecyl ketone, are chlorinated (in presence of a trace of I) to give, according to th e tem p, and am ount of CL>, mono-, di-, or higher chlorinated derivatives, which are lubricants of increased oiliness compared with the parent substances. N. H. H.
M a n u fa c tu re of a n th ra q u in o n e d e riv a tiv e s . A. Ca rpm ael. From I. G. Fa r b e n in d. A.-G. (B.P.
487,877, 30.12.36).—The interaction of CH2Ph*CN (I) with a 2-eyanoanthraquinone-3-carboxylic acid, its amide, or ester, or of CuCN and (I) with a 2-lialogcno- anthraquinone-3-carboxylic acid, its amide, or ester gives products (dye interm ediates) distinguished by a eomflower-blue vat. E.g., Me 2-chloroanthraquinone-3-carboxylate, CuCN, and excess of (I) a t tho b.p. for 2 hr. give a yellow Cl-free product, with interm ediate form ation of Me 2-cyaiwanthraquinone-3-carboxylate, m.p. 247°. Similar products are obtained from 2- chloroanthraquinone-3-carboxylic acid (m.p. 343—
344°) and its amide. H. A. P.
M a n u fa c tu re of h e te ro c y c lic n itro g e n c o m p o u n d s c o n ta in in g a ld e h y d e g ro u p s . G. W.
Jo h nso n. From I. G. Fa r b e n in d. A.-G. (B.P.
486,780, 9.12.36).—Cyclic N H 4 salts containing re active Me or th eir ^-bases are condensed with form- amidines N R IC H -N R'R" in which R and R ' are aryl and R " is alkyl, aryl, or aralkyl, or N R 'R " is p a rt of a saturated ring ; the polymethine dyes th u s obtained are split by alkalis with the form ation of aldehydes.
E.g., 2-methylquinoline etlnodide and diphenyl- m ethylform am idine, NPhiCH-NPhMe (I), give the
yellow dye (II), which with aq. NaOH (d 1-2) a t a X—CILCH-NPhMc 100° gives an aldehyde, m.p. 101— 102°, probably E t / \ t ,t t ,
l-ethyl-2-aldehydo-1 '■ methylenequinoline, and NHPhM e. Corresponding aldehydes are ob
tained from (I) and 1 : 2 : 3 : 3-tetram ethyl- indoleninium bromide (III), m.p. 117—118°, b.p.
170—172°/2 mm. (IV), 1-methylbenzthiazole m etho
sulphate, m.p. I l l — 112°, and 2-m ethyl-P-naphtha- thiazole m ethosulphate, m .p. 189— 190°. In te r
action of (III) w ith phenyl-2-methylindolinylform- amidine gives a bright yellow basic dye, split as before by alkalis to 2-co-aldehydomethylene-l : 3 : 3-tri- methylindoline [(IV) above] and 2-m ethylindoline;
similar products [5-Olfe-derivative of (IV), m .p.
107— 108°] are obtained with 5-m ethoxy-l : 2 : 3 : 3- tetram ethylindoleninium bromide. Similarly,
1 : 2 : 3 : 3-tetramethyl-(3-naphthindoleninium brom ide and phenyltetrahydroquinolylform am idine give a yellow basic dye of good light-fastness, converted by alkaline hydrolysis into an aldehyde, m.p. 152°,
and tetrahydroquinoline. H. A. P.
A p p a r a tu s fo r re a c tio n s b e tw e e n liq u id s a n d g a se s o r v a p o u r s .—See I. H y d ro c a rb o n s fo r m o to r fu e ls. A lk en e s fr o m h y d ro c a rb o n m ix tu r e s . P o ly b a sic a c id d e riv a tiv e s of h y d ro - fo rm e d n a p h th a s . H ig h -b o ilin g p o ly m e rid e s . P r o d u c ts fo r i m p a r ti n g c o lo u r etc. to lu b r ic a t
in g o ils.—See II. A n th ra q u in o n e etc. c o m p o u n d s. P h th a lo c y a n in e s .—See IV. C a ta ly s ts fo r o rg . s y n th e s is .—See V II. C o n d en satio n p r o d u c ts . P o ly m e ric a m id e s .—See X III. P r e s e r v a tio n of r u b b e r . V u lc a n isa tio n a c c e le r a to rs .—
See XIV. B u aO H -C O M e„-E tO H fe rm e n ta tio n s . Py-B utylene g lycol.—See X V III.
IV .- D Y E S T U F F S .
E le c tr o m e tr ic d e te r m in a tio n of free s o d iu m h y d ro s u lp h ite o r fre e in d ig o in re d u c e d in d ig o p r e p a r a tio n s . N. Straffo rdand W. V. St u b b in g s
(J.S.C.I., 1938, 5 7 , 242—245).—Both determ inations depend on the preferential oxidation of Na2S20 4 in presence of alkali salts of leucoindigo (I) by Fehling’s solution (II). A special apparatus is used from which air is displaced by purified N2. The course of the titratio n is followed potentiometrically. A full potentiom etric titratio n exhibits two sharply defined end-points, the first due to a considerable rise in oxidation-reduction potential as soon as all the N a2S20 4 has been oxidised, the second to a further considerable rise in potential as soon as all the (I) has been oxidised. Only tho first end-point is utilised in the determ inations described. For the N a2S20 4 determ ination, (II) is standardised in the same apparatus against a N a2S20 4 solution previously standardised by an established m ethod, e.g., by 0- lN-I. F or tho free indigo determ ination, a measured q u an tity (excess) of standard N a2S20 4 solution is added and, after “ v attin g ,” th e excess is determ ined as above w ith (II). In this case the N a2S20 4 solution is standardised by the same technique against standard indigo powder. The m ethod can be extended to the determ ination of th e to tal indigotin content of reduced indigo products which are free from interfer
ing substances, e.g., reducing sugars. In this case both potentiom etric end-points are utilised.
C o lo u r in te n s ity of d y e stu ff m ix tu r e s . G.
Szamek(Tech. K urir, 1938, 9 , 55—57).—The vals. are obtained b y adding the vals. (FA, F n, etc.) for the components \A , B , etc.) in proportion to their concn.
(Ca, Ob, etc.). F A + s = CaFa + Cj)FB + . . . . To com
pare the colour intensity of two dyes, to a g. of A p g. of “ chromoxide-green ” (I) m ust be mixed to obtain the colour intensity of b g. of B mixed with q g.
of ( I ) ; F a = F B{bqjap). E. P.
D ia z o su lp h o n a te s in te x tile p r in tin g .—See VI.
F lu o re sc e n c e a n a ly s is .—See X I.
See also A., II , 359, C o u p lin g m e th o n e w ith te tr a z o n iu m c o m p o u n d s. 364, a a n d p N a p h th
-oic a c id s . 370, A liz a ra te s . 378, D yes fr o m th io - h y d a n to in . 380, F la v in d u lin e d e riv a tiv e s.
Pa t e n t s.
P ro d u c tio n of m o n o azo d y es. Soc. Ch e m. In d. i n Ba sle (B.P. 487,621, 31.3.37. Switz., 31.3.36.
Cf. B.P. 424,354; B ., 1935, 717).—Diazo compounds derived from am inesp-N H 2U 6H 4-N(CH2Ph)-S02Ph (I) in which each of th e C6 nuclei m ay be substituted, e.g., bv halogen, alkyl, or alkoxy, are coupled with
Cf. B.P. 424,354; B ., 1935, 717).—Diazo compounds derived from am inesp-N H 2U 6H 4-N(CH2Ph)-S02Ph (I) in which each of th e C6 nuclei m ay be substituted, e.g., bv halogen, alkyl, or alkoxy, are coupled with