BRITISH CHEMICAL ABSTRACTS
B.—A PPL IE D CHEM ISTRY
JA N . 15 and 22, 1932.*
I.— GENERAL; PLA N T; MACHINERY.
P ractical m eth od s of d etectin g and d eter m in in g m e th y l chloride in [refrigerator] air and foods.
M. J. M a r t i n e k and W. C. M a r t i (Ind. Eng. Chem.
[Anal.], 1931, 3 , 408— 110).—Poisonous leaks ( > 1 pt.
in 100,000) may be detected by the blue-green flame produced on a heated cone of Cu gauze suspended over a small E tO H flame. In general, 50 p.p.m. or more of org. lialogen compounds m ay be detected by passing 200 c.c. of the gas mixture, filtered through NaOH-CaO, from a sample bottle through a quartz tube electrically heated to 1000°. The C 02 and HC1 produced are passed through aq. AgN03 and any tu rb id ity is noted. For its determ ination a m icroburette delivers the gas, and it is necessary to pass the products of combustion through aq.
H3As03 to reduce Cl oxides; contam inated foodstuffs, urine, etc. are aspirated from a heated container.
H. R. J e n s e n . A pplication of e lectricity to the m ea su rem en t of tem perature. P. M. H o g g (J. Inst. Elect. Eng., 1931, 70, 47—53).—A lecture.
W elding o r riv e tin g for a p p a r a tu s.—See X.
Quick freezing of fru it ju ic es.—See XIX.
Pa t e n t s.
C entrifugal separator. O. 6 . P a r d o and S. D.
F e r n a n d e z (U.S.P. 1,804,108, 5.5.31. Appl., 6.3.29.
Cuba, 15.5.28).—In a separator having helical blades driven a t different speeds to remove solid m atter, the edge of the blade is provided w ith a deep groove in which are inserted arcuate scrapers pressed outwards by bow springs. B. M. V e n a b le s .
Vapour fractionation. D. J . B e r g m a n , Assr. to U n i v e r s a l O i l P r o d u c t s Co. (U .S .P . 1,803,956, 5.5.31.
Appl., 22.4.27).— In a tower the reflux liquid passes downwards from one pool through a com partm ent containing a number of ejector devices to a free space above the next pool. The gases are drawn downwards by the jets of liquid, b u t their general direction is upwards as they are transferred from a free space to the second ejector com partm ent above by external pipes.
To obtain a larger reflux flow some of the liquid may be pumped upward and recirculated. B . M. V e n a b le s .
Cleaning of d ep h legm ators. L. C. H u f f , Assr.
to U n i v e r s a l O i l P r o d u c t s Co. ( U .S .P . 1,803,969, 5.5.31. Appl., 13.4.25.)—The trays of a tower are flushed clean by jets of a liquid different from th a t treated in the tower. The jets may be attached to a rotatable axial bus-pipe so th a t every p art of every tra y is swept.
B. M. V e n a b le s . Separation of finely-divided liq u id s from g a se s.
W. H. K n i s k e r n , Assr. to A t m o s p h e r ic N i t r o g e n
C o r f . (U.S.P. 1,803,854, 5.5.31. Appl., 14.10.26).—
The gases are passed downwardly, with m any changes of direction, between corrugated sheets which are provided with drainage gutters on the peaks of the corrugations. B. M. V e n a b le s .
Condensers for refrigerating s y s te m s . B r i t . T h o m s o n -H o u s to n Co., L t d . , Assees. of D. F. N e w m a n and Iv. H . H u y e t t f . (B.P. 361,S06, 22.4.31. U.S., 22.4.30).
Soft w ater for sh ip s etc.—See X X III.
I!.— FU EL; G A S; T A R ; MINERAL OILS.
D eterm in in g the true com p osition [u ltim ate a n alysis] of coal. F. S c h u s t e r (Brenustoff-Chem., J931, 1 2 , 425—426 ; cf. B., 1931, 827).—The coal is subdivided, e.g., by a float-and-sink m ethod, into two fractions, of low and high ash contents, respectively.
From these a suitable num ber of mixtures of ascending ash content are made (two mixtures of interm ediate ash content generally suffice), and each is subm itted to ultim ate analysis, including the direct determ ination of 0 , to tal S, and N. The vals. obtained are plotted against ash content and extrapolated to zero ash content to give the true composition. The true ash content is deter
mined by Brinsmaid’s method, and the H 20 content by Terres and K ronacher’s method (B., 1930, 1051).
A. B. M a n n in g . D eterm ination of sulphur in coal and coke.
G. V . L e r n e r m a n (J. Chem. Ind., Russ., 1931, 8, 1087—1089).—One g. of powdered coke or 0-5 g. of coal is mixed w ith 3 times its wt. of a 1 : 2 m ixture of N a2C03 and MnOa, the m ixture is burned in a current of 0 2, the residue is dissolved in H 20 , and S 0 4" is determined. R. T h u s z k o w s k i.
D eterm ination of sulphur in graphite. L . H a r a n t (Z. angew. Chem., 1931, 4 4 , 921—922).—The sample (1—2 g.) is heated to 1000° in a current of purified 0 2 and the evolved S 0 2 passed through 2-5% aq. AgN03, which is finally titra te d to methyl-red with 0-01A’- alkali, each mol. of S 0 2 liberating 2 mols. of acid. The method gives results in agreement with those based on ignition with Na3C03 and MgC03 or K M n04.
F. 0 . H o w i t t . E xperim ental error of the shatter te st [for coke].
H. V . A. B r i s c o e and C. B . M a r s o n (Fuel, 1931, 10, 464— 471).—From a study of the errors in four series of 48 shatter tests carried out on different samples of coke it is deduced th a t (a) errors of the mean of three tests having a probability of 1/11 for two Durham, one Cumberland, and one Scottish coke are 1-9, 2-2, 2-7, and 2-2 unite for the 2-in. index, and 0-8, 1-1, 1-9,
* The remainder of this set of A bstracts w ill appear in next week's issue. -
51 a
B r itis h C h em ica l A b s tr a c ts —B .
52 Cl. I I . — Fu e l; Ga s; Ta r; Mi n e r a l Oi l s.
and 2-0 units for the H -in. index, respectively; and (b) when comparing the means of three tests for each of two cokes of the same class, differences in the shatter index having a probability of 1 /101 for the above cokes are 2*9, 3-3, 4-0, and 3-3 unite for the 2-in. index, and 1-2, 1-7, 2-8 and 3-0 units for the 1 ¿-in. index,
respectively. A. B. M a n n in g .
Influence of inorganic constituents in the car
bonisation and gasification of coal. Inst. G as.
R es. F ellow ship R ept., 1 9 3 0 — 3 1 . A. II. E a s t w o o d and J . W. Cobb (Gas J., 1931, 1 9 6 , Suppl., 18—19).—
When coal is carbonised and the gases are led through a short plug of CaO or CaC03 maintained a t the same temp, as the coal, the yield of NH3 is the same as if the CaO were mixed with the coal, and considerably greater than th a t obtained in the absence of CaO. Tho effect of the CaO is therefore on vaporised N compounds expelled from the coal, and not on the coal substance.
A parallelism has been traced, (a) a t different temp., (6) a t different times a t each temp., between the libera
tion of N II3 and I I 2 from both coal and anthracite, and it is concluded th a t the compounds which produce these gases are either identical or decompose a t the same temp.
A. Ke y. Coal hydrogenation. I m p e r ia l Chem . I n d u s t r i e s , L t d . (Fuel, 1931, 10, 481— 184).—The process of hydro
genation of coal under pressure in the presence of catalysts is briefly outlined ; it involves the four steps, (1) manufacture of H 2, (2) liquid-phase hydrogenation, (3) vapour-phase hydrogenation, and (4) refining.
100 tons of dry, asli-free coal yield 62 tons of petrol, 28 tons of gas, and a residue containing the ash and 6 tons of solid carbonaceous material. The gas is used for the manufacture of H 2l and the residue for firing boilers. The over-all coal consumption is 3-15 tons (reckoned as dry and ash-free) per ton of petrol pro
duced. A plant costing 7—8 million pounds sterling could produce 210,000 tons of petrol per annum a t a cost of 7d. per gal. A. B. M a n n in g .
R otary-kiln flam e and its relation to coal, air, and coal ash. 0 . Frey (Cement, 1931, 4 , 1241—
1243),—The principal conditions for correct firing are the closest possible mixing of coal dust and air, the use of dry and evenly graded fuel, and the maintenance of even air pressure and draught, the former preferably by mechanical blowing. Too coarse grinding of the coal allows the larger particles to settle in the cooler portion of the kiln, preventing cooling of the clinker and causing high fuel consumption. The effect of extremely fine grinding is th a t the particles are burned rapidly and completely and molten globules of ash are blown far into the kiln, and cover the nodules of partly calcined material with a viscous skin, causing the mass to conglo
merate and hang up in the kiln. Medium-fine grinding assumes only a trace of residue on a 76-mesh screen and 8—10% on a 180-mesh. C. A. King.
C om bustion conditions in lu m in o u s flam es.
K. BtRiTE and A. L a n g (Gas- u. Wasserfach, 1931, 7 4 , 1073—1077).—The height, surface area, and vol. of flames of H 2, CO, CH4, mixtures of CH4 with H 2 and CO, and C2H 2- H 2 mixtures have been determined as functions of gas velocity and of the vol. of air required
for combustion, a t cylindrical jets (diam. 0-5—2 mm.).
The flame height for the same jet increased approx.
proportionally to tho gas velocity ; for the same gas velocity the heights of CH4, CO, and H 2 flames decreased in the order given. Referred to the vol. of air required for combustion, CO gave a relatively higher flame th an either C IIj or H 3, b u t the relative heights of the two la tte r varied w ith the diam. of the jet. Similar results were obtained with the gas mixtures. The I I 2 present in the gas and/or th a t produced by decomp, of the hydrocarbons present increases the rate of combustion and produces a smaller flame, owing firstly to its high rate of diffusion and secondly to its influence on ‘the mechanism of combustion which involves the formation of H atoms and OH radicals (cf. H aber and Bonhoeffer, A., 1929, 11). A. B. M a n n in g .
P roducts of com b u stion from typical g a s ap p li
ances. V I. O xides of nitrogen. R ept. 28 of J o in t R es. C om m ., In st. G as E ng. and U n iv. Leeds.
J . W. W o o d [with introduction by J . W. Cobb] (Gas J., 1931, 196, Suppl., 4—8 ; cf. B., 1930, 100).—C r03- H 2S 0 4 solution was used to absorb N oxides, these being subsequently reduced to N II3 and determined as usual (Nessler tube). The ratio N O /C 02 for free-burning flames wras about 0-001, being least for Méker and greatest for geyser burners. The am ount of NO was much less influenced by m aladjustm ent of the burner than was the CO production, and no exception could be taken to it on hygienic grounds. 5— 10% of the NO remained in the condensate from the flue gases, and this also contained 60—70% of the S in the gas and had a corrosive action. Other work on the subject, together with recent work on the production of CO in gas appli
ances, is reviewed. A. K e y .
Report on th e com b u stion standards of gas appliances. C. A. M a s t e r m a n and E. W. B. D u n n in g (Gas J., 1931, 196, Suppl., 9— 14).—Conclusions from tests on over 400 appliances are given regarding the production of w ater vapour, C 02, CO, and S 0 2 from the combustion of coal gas. The am ount of CO pro
duced is usually <[ 0-2 cu. ft. per therm. Quantities larger than this may be due to lack of excess 0 2 to the flame or to excessive gas rate. W ith a flueless modern appliance in an unventilated room the products of combustion would cause discomfort in the order water vapour (increased humidity), S 0 2, C 0 2, and CO.
Tho CO content would not approach the safe limit of 0-02% of the air until the previous stages were far
advanced. A. K e y .
O xide of iron purification of coal g a s. R. II.
C l a y t o n , H . E. W i l l i a m s , and H. B. A v e r y (Gas J., 1931,196, 311—315).—Equations are given representing 35 reactions which have been found to occur during dry purification of coal gas. I t is preferable to produce spent oxide rich in S. This can be attained by thé use of oxide containing an adequate am ount of moisture (35—40%), working conditions being such th a t the H 20 is retained in the oxide, absorbing the gaseous impurities, and bringing them into contact with the purifying material. Tar fog in the gas reduces the efficiency of the oxide and increases the back-pressure. Revivifica
tion of the oxide takes place more slowly th an fouling,
B r itis h C h e m ic a l A b s tr a c ts —B .
Cl. I I . — Fu e l; Ga s; Ta r; Min e r a l Oil s. 53
and excess of 0 2 (1%) is required. A const, small quantity of N II3 (e.g., i grains/100 cu. ft.) in the gas is sufficient to m aintain alkaline conditions in the purifiers, thus accelerating the purification. Visual tests for HCN and NH3 in gases are described. The former employs green NiC03, changing to yellow Na2Ni(CN)4, and NH 3 is determined by following the neutralisation of acid absorbed on cellulose in presence of bromophenol- blue. In modern English practice the oxide in each box purifies 25—30 times its vol. of gas per hr. The methods of working and controlling the purifiers are discussed. The oxide should be in such physical condi
tion as to expose a large surface of fully hydrated Fe oxide, b u t should not tend to crush under its own wt.
Present practice in Germany is reviewed. A. Key. D eterm in ation of hydrogen and m ethane [in coal g a s etc.] in the J a g e r -O r sa t apparatus u sin g cupric oxid e. E. D i t t r i c h (Gas- u. Wasserfach, 1931, 74, 1039—1040; cf. B., 1931, 791).—P auschardt’s simplification of the .lager method is criticised on the grounds th a t the t l 20 vapour produced by the combus
tion of CH4 is neglected, and th a t the method is inapplic
able to the higher homologues of CII4, a t any rate unless the reaction tube is very small. F urther, th a t such homologues are already burned a t the tem p, of com
bustion of H„ (380°). P auschardt states th a t the m ethod is intended only for the analysis of illuminating gas and th a t the effect of H 20 vapour is negligible.
C. I r w in . 3rd R ept. on u se o f [coal-tar] creosote in the m an u facture of carburetted w a te r -g a s. 29th R ept. of the J o in t R es. C om m ., In st. G as E ng. & U niv. L eeds.
F. J. D e n t (Gas J., 1931, 196, Suppl., 19—21 ; cf. B., 1931, 99).—Creosote has been cracked a t temp, and in atm . similar to those in carburetters of large-scale water- gas plants. Light creosote from vertical retorts gave a better therm al yield of gas than heavier creosote from horizontal retorts, b u t the yield was only one th ird to one half th a t given by gas oil, being 0 • 65 therm per gal.
a t 900°. 70—80% of the creosote reappeared as tar.
Dilution w ith gas oil did n o t result in an increased gas yield from the creosote. Cracking a t temp, above 900°
did not effect an improvement, and above 1100° the gas yield decreased. Above 1000° liquid ta r was not formed, b u t a sooty material am ounting to 70% of the creosote appeared. This material was very unreactive to steam, not being appreciably gasified a t 1300°.
Passing C10II8 over W wire heated a t 2000—3000°
yielded C2f i 2 and much C. Gas oil gave a max. gas yield when cracked a t 750—800°. Below this the yield of ta r was greater, and above 800° hydrogenation decreased the thermal yield. Under normal conditions an increased H 2 content of the atm . of cracking increases the therm al yield of gas, b u t a t higher tem p, a decrease
occurs. A. K e y .
1st R ept. of the [G as-]L iquor Effluents and A m m on ia S ub-C om m ittee [of the In stitu tion of G as E n g in eers]. A K e y [with introduction by J. W. Cobb]
(Gas J., 1931, 196, Suppl., 14— 16).— (a) A cyclone ta r extractor acting on hot crude coal gas w ith a min.
velocity of the gas a t the inlet of 20 ft./sec. resulted in 84% of the ta r condensed to the outlet of the condensers being brought down in the reto rt house. The subsequent
liquor had a greatly reduced higher ta r acid content, and the 0 2-absorption val. of the spent liquor was reduced by 21%. (6) Cresols are much more easily removed from H aO by org. solvents than is PhO II. Pyrocatechol, representing higher ta r acids, is difficult to remove.
Crude benzol is as effective a solvent for phenols as is 90’s benzol. Tritolyl phosphate is a very effective solvent for all phenolic substances, b u t aliphatic com
pounds are not effective, (c) In a countercurrent semi
scale washer crude benzol removed 44% of the phenols from ammonia liquor a t 12° and 69% a t 60°. The height of the washer is im portant. Up to 45% of the sulphide was also removed by the benzol. The methods of recovering benzol dissolved in the liquor are dis
cussed. (d) The degree of purification of spent liquor in bacteria beds is not influenced by the presence in the liquor of fixed NH3. (e) 16 gals, of spent liquor per ton of coal carbonised can be destroyed on the bars of step- grate producers, w ithout producing objectionable pro
ducts. The destruction of liquor in excess of this would be expensive in fuel. ( /) By working up circulating liquor to a high chloride content, and evaporating, com
paratively pure N H 4C1 can be obtained w ithout using acid. Ways of purification are discussed. A. K e y .
C atalytic dehydrogenation as a m ethod of in vestig a tin g the hydrocarbons of petroleu m . N.
D. Z e l i n s k i and B. A. K a z a n s k i (Ber., 1931, 64, [B], 2265— 2270).—Fractions, b.p. 170—200°, of Baku petrol
eum are passed a t a const, rate over 20% P t-C a t 300—
310°. About 30% of the fractions consists of hexaliydro- arom atic hydrocarbons readily converted a t P t-C into H 2 and arom atic hydrocarbons. The main portion is composed of cycZoparaffins, mainly ci/cZopentane deriva
tives which do not suffer catalytic dehydrogenation.
H . Wr e n. V isc o sity fall of lubricating o ils on d ilu tion . J. T a u s z and A. R a b l (Z. angew. Chem., 1931,44, 884—
886).— The formulae of Tausz and Staab (B., 1931, 187) and of Lees (Phil. Mag., 1906, [vi], 1, 123) are shown to be identical. The fall of viscosity of oils on dilution is probably due to the breaking up of mol. associates with change of vol. E. S. H e d g e s .
S o lu b ility of w ater in aviation g a so lin es. E. W.
A l d r i c h (Ind. Eng. Chem. [Anal.], 1931, 3 , 348—354).
—N a-K alloy free from oxide is added to the liquid saturated w ith H 20 and freed from dissolved gases, and the H 2 evolved is collected and measured. D ata are given for the solubility of H 20 in 5 aviation gasolines.
In general, the solubility of H 20 a t room temp, is about 1 in 10,000, increasing w ith rise of temp., and all commercial gasolines are normally saturated with H 20 when used in internal-combustion engines. The proce
dure is applicable to the determ ination of traces of H 20 in m any org. liquids. E. S. Hedges.
A cO H reco v ery in w ood d istilla tio n .—See III.
B leaching w ith N .Z . fu ller ’s earth .—See XII.
B itu m en s in p a in ts.—See X III. Coal a s fertiliser.
Irrigation [of p lots] w ith a m m on iacal liq u o r.—
See X V I.
Pa t e n t s.
R em oval of d u st from coal. S im o n -C a b v e s, L t d . , and V. H . A d a m s (B.P. 360,106, 5.9.30).—The coal is
a 2
B r itis h C h em ica l A b s tr a c ts —B .
54 Cl. I I . — Fu e l ; Ga s ; Ta r ; Mu t e r a i. Oi l s.
lowered gently down au inclined sieve, e.g., by means of a scraper conveyor or flexible metal sheet, and the small coal and dust which pass through the sieve are subjected to a current of air moving parallel to the sieve, which removes the dust. The small coal falls on to a plate inclined a t such an angle th a t the coal ju st slides down the plate under gravity.
A . B . Ma n n in g. D egasification of coal and sim ila r m a teria ls.
E. Kropiwnickx (B.P. 359,818, 14.1.31).— The material is fed continuously upwards through a vertical retort, e.g., by means of a worm in the lower part, thereof, a t such a rate th a t when it reaches the top of the reto rt and is a t its max. temp, it is completely degasified.
The retort is heated externally from the top by a down
wardly directed flame. The hot coke leaving the top of the retort falls down into vertical shafts wherein it is quenched by steam, the water-gas produced being mixed with the distillation gases and conveyed there
with to the gas purification plant. The quenched coke is partly or wholly discharged into a generator which supplies the gas used for heating the retort.
A . B . Ma n n in g. R egenerative coke oven s. H. R o w e r s A.-G.
(B.P. 359,482, 16.7.30. Ger., 27.9.29).—The oven is provided with two sets of regenerators lying below and parallel to the oven chambers and separated by a wall extending transversely to the oven chambers. The heating gases are so controlled th a t a t a particular moment all the regenerators on one side of the central wall are serving to preheat gas and air, while those on the other side are being heated by waste gases. The alternate regenerators of each set are subdivided by a partition parallel to the oven chambers, preferably in such a manner th a t a pair of smaller regenerators in one set is situated opposite an undivided regenerator in the other set. Each of the undivided regenerators com
municates by vertical ducts w ith the flues of two heating walls lying above it, and through a passageway extending over a regenerator of the opposite set, and branch passageways, with flues of four heating walls lying over the other set of regenerators. A. B. M a n n in g .
Ovens for carbonising [fuel] b riquettes. W. W.
W h i t e and H . D. P o n t e t (B.P. 359,476, 23.7.30. Cf.
B.P. 352,556 ; B., 1931, 871).—The oven comprises one or more horizontal stoving spaces arranged one above the other and separated by flues through which circulate hot gases from a fuel burner. The upper and lower walls of the spaces are of firebrick and are arched in form. The briquettes are charged on to sliding perforated trays from a feed hopper designed to charge the trays autom atically as they are run into the oven and to restrict the layer of briquettes to n o t more than two deep. The feed hopper is supported on a charging table of adjustable height, operated hydraulically.
After treatm ent the trays are withdraw n and the briquettes discharged, the base of each tray being pivoted to facilitate this operation. A. B. M a n n in g .
M anufacture of m etallu rgical coke. C. S t i l l (B.P. 359,869, 1.4.31. Ger., 3.4.30. Addn. to B.P.
356,079 ;. B., 1931, 1036).—Coals of high {e.g., 30%) volatile m atter content can be converted into satisfac
tory metallurgical coke when the heating walls of the oven are m aintained a t not above 850—900°.
A. B. M a n n in g . A pparatus for h an d lin g coke or oth er m a teria l of a friable nature. H . J . T o o g o o d , and R. D e m p s t e r
& S o n s , L t d . (B.P. 360,141, 30.9.30).—The coke bunker contains a side trough of spiral form ation w ith the opening facing tow ards th e central vertical axis of the spiral. The upper side of the trough is of the same width as the lower. The coke in the bunker enters the open side of the trough, the upper side of which forms a cover to support the superimposed stationary coke and to leave the interior p ath free for the descending coke in its passage to the zone above the bunker outlet.
A. B. M a n n in g . M anufacture of d eco lo risin g carbon. Y. In a da
(B.P. 360,200,12.11.30).—Wood or similar carbonaceous material is im pregnated with Ca(OII)2 by treatm en t with an aq. suspension of CaO, and is then carbonised.
The carbonised product is treated w ith sugar solution, which extracts the CaO as Ca saccharate.
A. B. M a n n in g . A ctivation of carbonaceous m a teria ls b y g a se s.
Soc. d e R e c h e r c h e s e t d ’E x p l o i t . P é t r o l i f è r e s (B.P. 359,546, 24.7.30. Fr., 9.9.29. Addn. to B.P.
358,940 : B., 1932, 8).—Two or more of th e activation retorts described in the prior p a te n t are used in con
junction, the treatm en t being carried out in alternate phases of heating and activation in such a manner th a t one of the retorts is a t the heating phase while a corre
sponding reto rt is a t the activating phase. Regenerators may be provided for enabling the waste heat in the gases leaving th e retorts a t the heating phase to be utilised in th e subsequent activation phase.
A. B. M a n n in g . D estructive h ydrogenation of carbonaceous m a teria ls. S t a n d a r d O i l D e v e l o p m e n t Co., Assees.
of R . P. R u s s e l l (B. P. 359,661. 22.9.30. U.S. 12.10.29).
—Heavy oils etc. are destructively hydrogenated under pressure in a prim ary reaction zone, and the vapours formed are p artly condensed under the same pressure in a rectifying apparatus, the condensate being returned to the reaction zone. The uncondensed vapours are passed to a secondary reaction zone wherein they undergo further destructive hydrogenation, preferably a t a higher temp., b u t under a lower pressure th an in the prim ary reaction zone. Catalysts may be employed.
A. B. M a n n in g . D estructive hydrogenation of carbonaceous m a teria ls. H . H a r p e r , R . S c o t t , and I m p é r i a l C iiem . I n d u s t r i e s , L t d . (B.P. 359,755, 17.11.30).—The vaporous reaction products are fractionated by passing through bubble plates arranged immediately above the level of the reaction liquid, and are then cooled by heat exchange with the relatively cool incoming I I 2. P a rt or all of the condensate is returned to the main body of reaction liquid. A. B. M a n n in g .
M anufacture of hydrocarbons b y destructive hydrogenation of coal su sp en sio n s, ta rs, m ineral o ils, etc . J . Y. J o h n s o n . F r o m I. G. F a r b e n in d . A.-G. (B.P. 359,993, 2.6.30. Addn. to B.P. 326,157 ; B., 1930, 498).—In the hydrogenation of materials
B r itis h C h em ica l A b s tr a c ts — B .
Cl. I I I . — Or g a n i c In t e r m e d i a t e s.
containing a catalyst in a state of suspension, settling of the catalyst is prevented by precluding the simul
taneous presence in the reaction m ixture of asphaltic substances and of hydrocarbons rich in H . Thus the initial m aterial is preferably freed from paraffin wax before treatm ent and th e reaction is so carried o u t th a t the products rich in H are continuously removed in the vapour phase. Coal tars may be distilled before tre a t
m ent in order to remove asphalt. A. B. M a n n in g . C onversion b y h eat-treatm en t of co a ls, tars, m in eral o ils, etc . J. Y. J o h n s o n . From I. 6 . F a k b e n in d . A.-G. (B.P. 359,945 and 359,983, 28.4.30).—
(a ) The materials to be hydrogenated are preheated before entering the reaction chamber b y being passed through a heating coil. Overheating is avoided by passing th e heating gases along the outside of th e coil in the same direction as th a t of the materials in the coil, and providing other means, e.g., a suitable variation in the size of th e heat-exchanging surfaces, or a reduction in th e heat conductivity of the tube along its length, for reducing the h eat transfer to the coil as th e temp, of the m aterial approaches the reaction tem p, (b) The preheating m ay be carried out in an electrically heated tube. The heating is so adjusted th a t a t th e outlet end of th e tube the tem p, of th e latter is not more than 25° above th a t of the material. A . B. M a n n in g .
C atalytic hydrogenation of carbonaceous m a ter ia ls. S t a n d a r d O i l D e v e l o p m e n t Co., Assees.
of J . M. J e n n i n g s (B.P. 360,201, 12.11.30. U.S., 20.11.29).— Oils are hydrogenated under high pressure a t temp, above 400°, and the products withdrawn from the reaction zone are m aintained in contact with a hydrogenating catalyst, e.g., M o03 and/or Cr20 3, and with H 2, while being cooled to 370° or lower.
A . B . Ma n n i n g. D ecom p osition under the action o f heat of a m ix tu re of m ethane or other hydrocarbons and w ater vapour. F. A . F. P a l l e m a e i i t s , and U n io n Chim . B e l g e , S o c . A n o n . (B.P. 360,148, 3.10.30. Addn.
to B.P. 343,172; B ., 1931, 433).—The apparatus described in the prior p a te n t is provided w ith a regenera
to r divided into two compartments, in which the gas for heating the reaction chamber and th e air for com
bustion, respectively, are preheated. In th e following phase of the process th e two com partm ents are heated in parallel by the converted gas leaving the reaction
chamber. A . B . M a n n in g .
R em oval of acetylene, or acetylen e hydrocarbons, from g a se s. J . Y. J o h n s o n . From I. G. F a r b e n in d . A.-G. (B.P. 359,421—2, 16.5.30).—(a ) The gases are passed a t 100—200° over a catalyst prepared from a mixture of Ni and Cr salts, oxides, or hydroxides, to which m ay be added up to 10% of Mn, Ag, Cu, etc., or compounds thereof. The C ^ j is hydrogenated or polymerised w ithout deposition of C on the c a ta ly s t:
oiefines are unaltered, (b) The gases are passed a t 200—600° over a catalyst consisting of or containing Mo and/or W, or compounds thereof. A difficultly reducible m etal oxide, e.g.. A1„03, m ay be added to the
catalyst. .. A . B. M a n n in g .
M anufacture of low -tem p eratu re carbonisation tar. J . Y. J o h n s o n . From I. G. F a r b e n in d . A.-G.
(B.P. 359,507, 19.5.30).—Carbonisation is carried out in an Fe retort, e.g., an inclined rotary drum carrying a large num ber of carbonising tubes around which heating gases are circulated, the Fe being coated internally with Zn, Sn, or Pb, so th a t direct contact of the Fe with the coal etc. is avoided. Corrosion is thereby diminished and the proportion of asphaltic substances in the tar is decreased. A. B. M a n n in g .
D ecom p osition and h ydrogenation of heavy organ ic com pounds to produce lig h t hydrocarbons.
J . M. F . D. F l o r e n t i n and A. J . K l i n g (B.P. 357,822, 27.10.30. F r., 9.11.29).—Carbonaceous m atter (tar, carbolic oils, C10II8 oils) is first heated under high pressure, e.g., a t 450— 480°/500 atm ., to avoid premature decomp., and is then treated with H 2 a t lower temp, and pressures, e.g., 450°/250 atm . The reaction vessel is filled with pumice etc., which m ay carry catalyst.
C. H o l l i n s . A pparatus [trucks] for charging cham ber ovens for m a k in g coke and g a s. C. S t i l l (B.P. 360,834, 6.8.30. Ger., 9.8.29).
P ortable g a s producers. J. G o h in (B.P. 361,174, 31.12.30. F r., 31.12.29. Addn. to B.P. 323,147).
Vapour fractionation.—See I. W etting etc. agen ts.
A lk ali-m etal sa lts of fatty acid s from oiefin es.—
See III. Sulphates from su lp h ites etc. CO and H 2 from CH4.—Sec VII. C orrosion-retarding com pound.—See X. C electrod es.—SeeXI.
III.— ORGANIC INTERMEDIATES.
D eterm ination of butyl and eth y l alcoh ols in m ix tu r es. C. II. W e r k m a nand 0 . L. O s b u r n (Ind. Eng.
Chem. [Anal.], 1931, 3,387—389).—Determination of the composition of mixtures of E tO H and BuOII in dil. aq.
solution is carried out by oxidation with K 2Cr20 7 and 85% H 3P 0 4, under narrowly defined limits, distillation of the AcOH and butyric acid formed, and determining their to ta l am ount by titration and relative amounts by partition between H 20 and P rs20 . Curves are given from which the relative am ounts of the alcohols m ay be read off when the percentage partition coeffs.
are known. The method is limited in its application, b u t is fairly accurate. J . D. A. J o h n s o n .
Influence of m odern acetic acid recovery m eth od s in th e therm al req u irem en ts of w ood distillation.
B. v o n T e t j i a j e r (Chem.-Ztg., 1931, 55, 881—883).—
Methods for recovery of AcOH by distillation, such as the Charles process which employs a wood-tar distillate as “ entrainer ” for H 20 , besides saving all expense for CaO and H 2S 0 4 and increasing the yield of AcOH from 50% to 80%, have greatly reduced the fuel costs.
In the Charles process, which is entirely continuous, the only pumping required is for the elevation of the crude AcOH and for feeding cooling coils. Steam requirements for concn. are given as 1 - 7 kg. per kg. of crude AcOH, or for the whole process a max. of 4 kg.
a t 6 atm . To this figure about 10% m ust be added for pumping. I t is calc, th a t by using superheated steam and a back-pressure turbine, rather under 1 ton of fuel will be required for each ton of crude AcOH produced in the plant. C. I r w i n .
B r itis h C h em ica l A b s tr a c ta—S .
50 Cl. I I I . — O r g a n i c I n t e r m e d i a t e s .
D eterm ination of acetone in ad m ixtu re w ith other organic solvents b y the use of hydroxylam ine hydrochloride. M. K r a j c i n o v i c (Chem.-Ztg., 1931, 55, 894—895).—C0Me2 in presence of either EtOH, MeOIi, C6H6, EtOAc, technical benzine, or mixtures of these solvents, may be satisfactorily determined by addition of a known wt. to a solution of N H 20H,HC1 followed by titration with 0-1 A’-NaOH using methyl- orange as indicator. E. H. S h a r p i.e s .
Ether explosions and “ ether p eroxid e.”
Autoxidation of ether. A. R i e c h e (Z. angew. Chem., 1931, 44, 896—899).—Since peroxide appears in com
mercial E t20 when it is exposed to daylight in glass vessels, and yet pure E t20 absorbs only in the extreme ultra-violet, a sensitiser m ust be present in the commercial material. MeCHO is probably the active substance, and the accelerated peroxidation of E t20 in which peroxide has been destroyed, with the produc
tion of MeCHO, is thus explicable. The various hypo
theses regarding the nature of the peroxide and its mode of formation are reviewed. H. F . G i l l b e .
T e st for aldehydes, u sin g dim ethylcycZ ohexane- dione [“ dim etol W. W e i n b e r g e r (Ind. Eng.
Chem. [Anal.], 1931, 3, 365—366).—The condensation products formed when a 5—10% alcoholic solution of
“ dimetol ” is added to neutral or very faintly acid aq.
or aq.-alcoholic aldehydes are characteristically cryst.
and may be used for the identification of aldehydes.
The test is reliable, very sensitive, and simple, and serves to distinguish aldehydes from ketones. A table of m.p. of the products from various aldehydes is given. J . D. A. J o h n s o n .
EtOH recovery from celluloid m anufacture.—
See V. D eterm ination of paraform .—See XVI.
Pa t e n t s.
Manufacture of m onoethanolam ine [[3-amino- eth yl alcohol] dinitrate or its h om ologu es. J . Y.
J o h n s o n . From D y n a m it A.-G. v o rm . A. N o b e l & Co.
(B.P. 357,581, 23.6.30).— 6-Am inoettyl alcohol, pre
ferably as nitrate, is esterified w ith 95— 98% H N 0 3 a t 0° to — 10°, and the ester is then pptd. by pouring into E tO H or E t20 or a mixture of the two, a t the same temp. The OA7-dinitrate separates cryst. in good yield.
The excess H N 0 3 may be distilled off in vac. before
pptn. C. H o l l i n s .
Production o f alkyl chlorides. W. W. T r ig g s . From E. I. D u P o n t d e N e m o u r s & Co. (B.P. 357,528, 21.3.30).—A mixture of HC1 and an alcohol vapour (below C4), e.g., exit gases from H 2S 0 4, N a C l, and the alcohol in the usual manufacture of alkyl chlorides, is passed into aq. ZnCl2 (or other metal chloride catalyst)
kept a t 135°. C. H o l l i n s .
M anufacture of condensed products [glycoll- aldehyde, trioses, and tetroses] from form aldehyde.
L. O r t h n e r (B.P. 357,566, 19.6.30. Ger., 19.6.29).—
4% aq. CH20 is boiled with Pb(OH)2 or other alkaline agent under reflux until the reducing power (cold Fehl- ing s solution) reaches a max. From 12 kg. of CH20 are obtained 1-3 kg. of glycollaldehyde, 2-2 kg. of dl- threose, and 4-2 kg. of ¿Z-erythrose, which m ay be
separated after reduction to glycol, glycerol, and
erythritol. C. H o l l i n s .
Continuous production of pentaerythritol. J.
M e i s s n e r (B.P. 357,783, 25.9.30. Ger., 28.9.29).—
Solutions of MeCHO and CII20 and a condensing agent [NaOII, Ca(0H )2] are introduced a t 25°, through a series of mixing vessels, into a reaction chamber where they are stirred a t 50°, the temp, being regulated by jackets. The liquor leaves the chamber through an overflow, the time of reaction being about 2 hr. The yield is 80% on the MeCHO. C. H o l l i n s .
Production of saturated alcoh ols of h ig h m ol.
w t. D e u t s . I I y d r i e r w e r k e A.-G. (B.P. 355,484, 5.8.30. Ger., 3.8.29).—Waxes etc., hydrogenated to an I val. about 0, are hydrolysed w ith alkali and high-mol.
alcohols are extracted, e.g., with C2IIC13, or are separated by steam-distillation in vac. Suitable starting materials are sperm oil (giving cetyl and octadecyl alcohols), carnauba wax, beeswax, ocotilla wax, and wool fat.
C. H o l l i n s . [M anufacture of] w ettin g, penetrating, foam in g, and d isp ersin g ag en ts. H . T. B o h m e A.-G. (B.P.
357,649 and 357,650, 20.5.30. Ger., 10.7.29. Cf. B.P.
341,978 ; B., 1931, 290).—A sulphonated di- or poly- hydric alcohol above C10, e.g., sulphonated octadecylene glycol, is added to improve the wetting properties etc.
of liquid or plastic preparations for use in (a ) boring oils, dust-binding agents, (b) salves, creams, or vasenol
substitutes. C. H o l l i n s .
M anufacture of alk ali-m etal sa lts of fatty acids [from oiefines]. H . D . E l k i n g t o n . From N. V.
d e B a t a a f s c h f . P e t r o l e u m M a a t s . (B .P . 355,866, 19.6.30).—C2H 4 or other olefine is heated w ith H 20 and alkali or alkali phenoxides, naphthenates, or other weak-acid salts, e.g., a t 360°/46 atm . The H 2 liberated hydrogenates phenols, naphthenic acids, oleic acid, etc. when present. E tO H or other diluent may be used ; E tO II is converted into AcOH. From 2 litres of C2H 4 a t 20°/25‘5 atm . heated a t 400° with aq. K O H there are obtained 48 litres of I I 2 and 71 -5 g. of AcOH.
C. Ho l l in s. Introduction of active o x y g en into organ ic c o m pounds. G. S c h o n b e r g (B.P. 357,721,11.8.30. Austr., 10.8.29).—Active org. peroxides are obtained from men
thol, menthone, thymol, paraformaldehyde, etc. by treatm ent with a perphosphate (prepared, e.g., from H 20 2 and cryst. N a2P 40 7) or a m ixture of II 20 2 and a
pyrophosphate. C. H o l l i n s .
Production of arom atic a m in es. G. F. H o r s l e y , and I m p e r ia l C hem . I n d u s t r i e s , L t d . (B.P. 355,715, 27.5.30).—In the production of arylamines from phenols of the C6H 6 series and NH3, or prim ary or sec. amines (except diarylamines) there is used as catalyst a chloride of a metal capable of forming more than one chloride.
Examples a r e : N II2Ph from PhO II, dry NH}, and hydrated FeCl2 a t 380°/96 atm . for 6 h r . ; o-toluidine from o-cresol, NH3, and anhyd. FeCl3 a t 380°/120 atm .
for 12 hr. C. H o l l i n s .
M anufacture of o-am in oth iop h en ols. I m p e r ia l C hem . I n d u s t r i e s , L t d . , and C. H. L u m s d e n (B.P.
355,808, 29.5.30).—A 2-thiolarvlenethiazole is heated
B r itis h C h e m ic a l A b s tr a c ts —B .
Cl. I V . — Dt e s t c f f s. 57
with 5— 10% teq. XaOH a t 180—210" in a closed vessel.
The prep, of o-aminothiophenol, 2-amino-5-ethoxy- thiophenol, and 2-amino-a-thionaphthol is described.
C. Ho l l in s. M anufacture of 2-m ercaptobenzthiazoIe and its m eth y l h o m ologu es. G o o d y e a r T ik e <fc R u b b e r Co.
(B P. 357,760, 15.9.30. U.S., 6.11.25).—.YiY-Diphenyl- methylenediamine is converted into 2-thiolbenzthiazole by the action of CS2 and S a t 230—260'/25—50 atm . The tolyl and xylyl compounds behave similarly.
C. Ho l l in s. M anufacture of [n on -resin ou s] condensation products of form ald eh yd e w ith a rom atic sulphon- am id es and AT-arvl d erivatives thereof, and th eir application a s p la stic isers. M o n s a n t o C hem . W o r k s , Assees. of A. L. E i s p l e r , M. L c t h y , and F. E.
S c h i l l i n g (B.P. 349,956, 31.12.29. U .S ., 31.12.28).—
Arylsulphon-amides and -arylamides are condensed w ith CH20 in presence of a little H 2S 0 4, ZnCl2, etc.
a t 100—1503, or a t 60— 120’ in AcOH. The product from ^-toluenesulphonaniide has m.p. 160—170°, from benzenesulphonamide, m .p. 215— 220°; they are plas
ticisers for cellulose nitrate, acetate, etc. 0'. H o i. l in s . M anufacture of in term ed iates and d y es from h eterocyclic nitrogen com p ou n d s [and a p p lica
tion a s photograp h ic se n sitise r s]. I m p e r i a l C hem . I n d u s t r i e s , L t d . , H. A. P i g g o t t , and E. H.
R o d d (B.P. 355,693, 24.2. and 31.5.30).—Heterocyclic N compounds carrying reactive Me or external CH2 groups are condensed with 1 mol. of a compound, A rX H -[CH]nINR, where A r is aryl, R any substituent, and n an odd num ber > 1, to give interm ediates, which are further condensed w ith similar heterocyclic com
pounds or w ith a cyclic compound having in fact or potentially a reactive CH2 group as ring-member {e.g., a pyrazolone, or an indole with unsubstituted 3-position), to yield photosensitising dyes. Similar dyes are obtained in the first-mentioned reaction by using 2 mob. of the heterocyclic compound. Examples a re : 2-methylene-l : 3 : 3-trimethylindoline with' 0-5 mol. of s-anilino-a-phenylim ino-A^-pentadiene hydro
chloride in Ac20 (green on tannined cotton ; sensitises emulsions to X 750—900 m o .); 2 : 3 : 3-trim ethyl- indolenine methiodide w ith {J-anilinoacraldehyde anil, and the interm ediate so obtained condensed w ith 2-methylbenzthiazole ethiodide (greenish-blue); 2 : 3 : 3 - trimethylindolenine methiodide w ith fi-anilinoacralde- hyde anil and then with 2-methylindole (lavender-blue).
C. Ho l l in s. M anufacture of a ry la m id es of a rom atic hy d ro x y - carb oxylic a c id s. W. W. G r o v e s . From I. G.
F a r b e n in d . A.-G. (B.P. 355,328, 21.5.30. Addn. to B.P. 336,428 ; B., 1931, 58).—The arylaminocresotic acids of the prior p aten t are converted into arylamides having good affinity for cotton fibre. Examples a r e : 3-hydroxy-6-methyldiphenylamine-2 (or 4)-carboxyl anilide, m.p. 170°, p-nitroanilide, m.p. 225°, p-toluidide, m.p. 152°, p-chloroanilide, m.p. 186°, ^-anisidide, m.p.
180°, o-anisidide, m.p. 152°; 3-hvdroxy-4': 6-diphenyl- amine-2(or4)-carboxyl anilide, m .p. 219°, o-anisidide, m.p. 150—151°, jj-chloroanilide, m.p. 203—20-1°;
4'-chloro-3-hydroxy-6-methyldiphenylamine-2- (or 4-) carboxyl anilide, m.p. 183°, ¡3-naphthylamide, m.p.
211°, 7>-nitroanilide, m.p. 255°, p-chloroanilide, m.p.
203°, p-anisidide, m.p. 178°, o-toluidide, m.p. 185°;
o-anisidide, m.p. 158°, »i-nitroanilide, m.p. 231° - 4'-chloro-3-hydroxy-5-methyldiphenylamine-2- (or 4-) carboxyl »i-nitroanilide, m.p. 145°, anilide, p-chloro- anilide, m.p. 159°, and ^-naphthylam ide, m.p. 168°.
0 . Ho l l in s. M anufacture o f p o ly m e risa tio n products [from sty r en es]. I. G. F a r b e x i x d . A.-G. (B.P. 355,573, 17.10.30. Ger., 28.1.30).—The polymerisation of aq.
emulsions of styrene or its homologues is catalysed by 0 2 or substances supplying 0 2 (e.g., H 20 a). C6H 6-sol.
products are obtained below 80°. C. H o l l i n s . M anufacture of polychloronaphthalenes. Im p e
r i a l C hem . I n d u s t r i e s , L t d . , F. H o l t , R . T h o m a s, and C. W. R i c h a r d s (B.P. 3 5 7 ,7 4 3 , 2 9 .8 .3 0 ).— CK,H 8 is chlorinated in presence of a halogen carrier first a t
85— 1 1 0 ° to a monochloro-compound and then a t
140— 150°. C. H o l l i n s .
M anufacture of anthraquinone d eriv a tiv es. A. G.
B lo x a m . From Soc. Chem . I n d . i n B a s l e ( B .P . 355,657, 25.4.30. Addn. to B.P. 353,932; B„ 1931, 1133).—
In the process of the prior patent, any sulphonic group ortho to an a -0 H group is elim inated during the anima
tion. Examples are : 1 : 4 : 5 : 8-tetra-am inoanthra- quinone and 4 : 8-diamino-l : 5-di(methylamino)anthra- quinone from leucodiaminoanthrarufin-2 : 6-disulphonic acid ; 4 : 5-diamino-l : 8-di(methylamino)anthraquinone from leucodiaminochrysazin-2 : 7-disulphonic a c id ; 1 : 4-di(methylamino)anthraquinone from leucoquin- izarin-2-sulphonic acid. C. H o l l i n s .
M anufacture of c arb oxylic acid d erivatives of the anthraquinone se ries. I. G. F a r b e n in d . A.-G.
(B.P. 355,597, 12.11.30. Ger., 12.11.29. Addn. to B.P. 277,670; B., 1928, 922).—Anthraquinones con
taining a 2-Me group and a 1 : 9-heterocyclic ring are oxidised to carboxylic acids by the process of the prior patent. Examples are carboxylic acids from 4-methyl- pyrazolanthrone, 4-methylthiazolanthrone (m.p. 205—
206°), and 4-m ethylthienanthrone. C. H o l l i n s . M anufacture o f am inodiazoanthraquinon es and of anthraquinone d erivatives therefrom . I. G.
F a r b e n in d . A.-G. (B.P. 355,464, 17.7.30. Ger., 17.7.29.
Addn. to B.P. 264,879 ; B., 1928, 8).—2-Halogeno- and 2 : 3-dihalogeno-l : 4-diaininoantluaquinones give mono- diazo compounds when treated with N a X 0 2 in 96%
H 2S 0 4. From the products there are obtained by Sandmeyer reactions (etc.) 2- and 3-bromo-l-amino- anthraquinone, 2 : 3-dichloro-l-aminoanthraquinone, m.p. 219—221°, 2 : 3 : 4-trichloro-l-aminoanthraquinone, m.p. 244°, 2 : 3-dichloro-l-ainino-4-cyanoanthraquiuone, m.p. 301—303°, 2 : 2' : 3 : 3'-tetrachloro-4 : 4'-diamino- 1 : l'-dianthraquinonyl, m.p. 380° (decomp.).
C. H o l l i n s . L ight hydrocarbons from heavy org. com p ou n d s.
—See II. T h io in d o x y ls.—See IV.
IV .-D Y E S T U F F S . Lake p ig m e n ts.—See X III.
Pa t e n t s.
M anufacture of su b stan tive d y es of the stilbene se r ie s. C hem . F a b r . v o r m . S a n d o z (B.P. 355,783,
B r i ti s h C h e m ic a l A b s t r a c ts— B .
iiS Ql. IV .—Dykstuffs.
27.3.30. Ger., 30.3.29).—Dinitrostilbenedisulphonic acid is condensed w ith sulphonic acids of dchydrothio- toluidine, primuline, etc. and the product is oxidised, e.g., w ith alkaline hypochlorite, to give direct yellows
and oranges. O'. H o l l i n s .
M anufacture of acid w ool d y es of the anthra
quinone se rie s. W. W. G r o v e s . F r o m I. G. F a r b e n in d . A .-G . (B.P. 355,697, 355,716, 355,743, and 355,810, [a ] 26.4.30, [b] 27.5.30, [c] 28.5.30, [d ] 29.5.30).
- —A 4-halogeno-l-aminoanthraquirionc-2-sulphonic acid is condensed with (a ) 5 : 6 : 7 : 8-tetrahydro-[i-naphthyl- ainine-4-sulphonic acid, (b) an aminodiarylmethane-2'- carboxylic acid, or (c) an o- 3-aininobenzoylbenzoic acid ; or (b, c) a 2 : 4-dihalogeno-l-aminoanthraquinone is thus condensed and the 2-lialogen atom is exchanged for S 03H. (b) The products m ay be cyclised. (d) The dyes of (b) arid (c) are improved in fastness to fulling by esterifieation of the C 02H groups. Examples of second components are (a) 5 : 6 : 7 : 8-tetrahydro-p- miphthylamine-4-sulphonic acid (green-blue); (b) 2- aminodiphenylmetliane-2'-carboxylic acid, m.p. 135—
136° (b lu e; cyclised, grey-black), the 4-amino-com
pound, m.p. 174—175° (green-blue ; cyclised, grey- black), 3-aminodiphenylmethane-2 : 4-dicavboxylic acid (b lu e; cyclised, blue-green), or 4-chloro-2-amino- diphenylmethane-2'-carboxylic acid (b lu e ; cyclised, b row n); (c) o-3'-aminobenzoylbenzoic acid (blue), o-(2-amino-4-toluoyl)benzoic acid (blue), or 3-amino- benzophenone-2': l-dicarboxylic acid (blue).
C. H o l l i n s . M anufacture of (a) hyd roxyth ion ap h th en s [thio- in d oxyls] and (a, b) d y es of the thioindigo ser ies.
1. G. F a r b e n in d . A.-G. (B.P. 355,661 and Addn. B.P.
355,662, 19.5.30. Ger., 18.5.29).—(a) 4-Halogeno- thioindoxyls are synthesised and are oxidised to the thioindigos : e.g., 4-chlorotliioindoxyl, m.p. 119— 120°, from 3-chloro-2-carboxyphenylthioglycollic acid, gives 4 : 4'-dichlorothioindigo (red). "(b) A 4-halogeno- thioindoxyl is condensed w ith a thioisatin a-auil etc., or a 4-halogenothioisatin a-anil with a thioindoxyl.
Examples a r e : 4-chlorotliioindoxyl with the a-p- dimethylaminoanil of 6-chloro-, 6-chlpro-4-methyl-, or 4-methyi-thioisatin. C. H o l l i n s .
M anufacture of a stab le, w ater-solu b le sulphuric acid ester from 4 : 6-d ich loro-6'-m eth oxy-b isth io- naphthenindigo [-thioindigo]. A. C a r p m a e l. From I. G. F a r b e n in d . A.-G. (B.P. 357,592, 25.6.30).—The leuco-compound is treated with S 0 3 (etc.) in presence of a tert. base. The product gives scarlet shades on
textiles. C. H o l l i n s .
M anufacture of a [thioindigoid] vat d ye con
taining sulphur. A. C a r p m a e l. F r o m I. G. F a r b e n in d . A.-G. (B.P. 357,593, 25.6.30).—A light-fast, ruby-red v a t dye is obtained by condensing 4 : 6-di- chlorothioindoxyl with thioisatin a-anils, chloride, etc.
C. H o l l i n s . V at d y es [of the indanthrone se r ie s]. N e w p o r t Co. (B.P. 357,536, 18.6.30. U.S., 1.7.29).—B r is dis
placed from 3-bromoindanthrones by chlorinating agents to give blue v at dyes faster to Cl2. 3 : 3'-Dlbromo- indanthrone is treated with 2-3 mols. of S 0 2C12 in
P h N 0 2 a t 70—75° for 60—90 min. and then a t 205—
210°. The B r is n o t completely displaced.
C. Ho l l in s. Preparation of azo d y es [b iological sta in s ; a n tisep tics]. L . M e l l e r s i i - J a c k s o n . From O s t k o R e s e a r c h L a b o r a t o r i e s (B.P. 355,380, 28.5.30).—
Biological stains of low toxicity (and th u s suitable for foodstuffs) are obtained by coupling a diazotised alkoxyaniline with wi-phenylenediamines. Examples are : p-phenetidiue -> m-phenylenediamine, m.p. 157—
158°, and the corresponding methoxy- (m.p. 157—158°), propoxy- (m.p. 133—134°), butoxy- (m.p. 127—130°), and amyloxy- (m.p. 112°) -compounds. The dyes stain all germs including the Koch bacillus, and are antiseptic (at a concn. of 1 in 25,000 the OEt-compound kills Staphylococcus albus and aureus and Streptococcus
hannohjticus). C. H o l l i n s .
M anufacture of m etalliferou s d y e s. Soc. Ciiem.
I n d . in B a s l e (B.P. 355,800, 28.5.30. Switz., 28.5.29.
Addn. to B.P. 343,014 ; B ., 1931, 580).—o-Hydroxyazo dyes, free from S 0 3H , S 0 2N H 2, substituted sulphon- amide groups, or C 0 2H groups, are boiled with sus
pensions of 1 or more m etal (except Cr) compounds, e.g., oxides, hydroxides, carbonates, or sulphides of Cu, Co, Ni, Mn, Fe, Al, Zn, to give products suitable for varnishes. Examples are : 4-nitro-o-aminophenol ->
resorcinol, w ith Mn20 3 (brown), F e20 3 (red), Fe30., (black-brown), or Ni20 3 (brown-orange) ; 4-chloro-o- aminophenol -> l-phenyl-3-methyl-5-pyrazolone, with Fe(OH)3 (green-yellow), or -> p-naphthol, w ith Fe(OH)3 (brown-black), or resorcinol, with ZnC03 (brown-
yellow). C. H o l l i n s .
M anufacture of m etalliferou s d y es [for v isco se silk s]. Soc. C hem . I n d . i n B a s l e ( B .P . 357,543, 20.6.30. Switz., 20.6.29).—Azo dyes, obtained by coup
ling J-acid alkaline with a diazotised o-aminophenol, and acid w ith a diazotised aminobenzoic acid, are treated with agents yielding metal. The products give level shades on viscose silks. Examples of diazo components are : 5-nitro-o-aminophenol and anthranilic acid (chromed, grey-blue); 6-nitro-o-aminophenol-4- sulphonic acid and anthranilic acid (chromed, grey-blue ; coppered, grey) or «i-aminobenzoic acid (chromed, neutral g re y ); 4-chloro-o-aminophenol-6-sulphonic acid and anthranilic acid (grey). C. H o l l i n s .
M anufacture of m onoazo d y es insoluble in w ater [p ig m en ts and ice co lo u rs]. W. W. G r o v e s . From I. G. F a r b e n in d . A.-G. (B.P. 355,709, 23.5.30).—
Suitable diazo compounds are coupled w ith aroylacetic arylamides in substance or on the fibre to give reddish- to greenish-vellow dyes. Examples are : benzoylacet- o-chloroanilide with 5-nitro-o-toluidine ; th e o-toluidide w ith 5-nitro-o-anisidinc; the anilide with 4-chloro-o-nitro- aniline : •p-chlorobenzoylacetanilide with 5-nitro-o-tolu
idine ; a-naphthoylacetanilide with 5-nitro-o-anisidine,
etc. C. H o l l i n s .
M anufacture of d isazo d y es [for regenerated cellu lose m a te r ia ls]. I m p e r i a l C hem . I n d u s t r i e s , L t d . , and R . B r ig h t m a n (B.P. 355,733, 22.5.30).—Dyes giving level shades on viscose silk are obtained by tetrazo- tising a pja'-diamine, N H 2A r■ X • A r-N H , (X being O, S,
