C ata ly tic o x id a tio n of h y d ro c a rb o n s in th e v a p o u r p h a s e a s a so u rc e of te c h n ic a lly v a lu a b le
p r o d u c ts . W . v o n Pio t r o w s k i and J . Wi n k l e r
(Petroleum, 1938, 3 4 , No. 16, 1—3).—A m ixturo of hydrocarbons of d 0-770—0-850 and b.p. 170—:250°
is vaporised in preheated air and passed through a reaction chamber packed w ith contact m aterial;
the reaction temp, is 260—300°. The products are condensed and fractionated; th ey consist of u n saturated hydrocarbons w ith one or two double link
ings, arom atic hydrocarbons, saturated and unsatu r
ated aldehydes and ketones, lactones, alcohols, and small quantities of carboxylic acids and phenols. The lightest and heaviest fractions have th e highest 0 content. The products find application (a) for odor- ising gas (cf. B., 1932, 488), (b) as a denaturant for EtO H , and (c) as agents for th e prevention of c 10h 8 and gum deposition in gas mains (cf. B., 1933, 611).
A. B. M.
C ata ly tic p o ly m e ris a tio n of eth y le n e a t a tm o s p h e ric p r e s s u r e . V I. P o ly m e ris a tio n a c tiv ity of ir o n c a ta ly s t. V II. Q u a lita tiv e t e s t on p o ly m e ris a tio n a c tiv ity of n ic k e l c a ta ly s t. V III.
S elective a c tiv ity of th e c a t a l y s t ; c o n s id e ra tio n s r e g a r d in g th e p o ly m e ris a tio n m e c h a n is m . Y.
Ko n a k a (J. Soc. Chem. Ind. Jap an , 1938, 4 1 , 22-—
23b; cf. A., 1937, I I , 438).—V I. Ignited F e(N 03)3 catalyst was inactive (300—400°). Fe2(C03)3 re
duced a t 480° gave small am ounts of polymeride a t
>300°. F e-C u-U 30 8 catalyst was best, and gave 1-7 c.c. of oil from 16 1. of C2H 4 (4 hr., 350°). Alkalis decreased the activity of Fe catalysts.
V II. Ni catalysts (pptd. by K 2C 03) were very active a t 240—270°. The effect of precipitants was in the order K 2C 03 > K O H > Na2C 03 > burned catalyst
> NaOH > aq. N H 3. Addition of inactive oxides, - e.g., of Pb, Cu (> 3 % ), Ag, destroyed tbe activity.
U30 8, C r03, MnO, and A120 3 (< 1 5 % ), and the Ni-M n series (particularly in presence of U30 8 or A120 3) were promoters.
V III. The polymerisation is a selective catalytic phenomenon. The reduction tem p, of NiO by H 2 is lowered by other oxides, particularly by those of Cu and U, b u t th a t of U prom oted and of Cu inhibited polymerisation, so th a t activity m ust depend mainly on the crystal structure. Polymerisation is a com
plex therm al reaction involving dehydrogenation, hydrogenation, and polymerisation. About 2—3%
of C2H 2 is present throughout the reaction, and is probably an essential interm ediate product. B u ta
diene was not detected. I. C. R.
S ta b ility of b u ta d ie n e a t d iffe re n t te m p e r a tu r e s in p re se n c e of L e b e d e v 's c a ta ly s t (co m p lex c a ta ly s t fo r s y n th e s is of b u ta d ie n e f r o m e th a n o l).
I. A. Vo l s h in s k i, G. M. Ko g a n, and 0 . M. NeIm a r k
(Sintet. K autschuk, 1936, No. 1, 4— 8).—The catalyst decreased the stability of (CH2!CH,)2 a t 500°.
Ch. Ab s. (c) N ew la rg e -s c a le o rg a n ic s y n th e s e s . G. Na t ta
(Chim. e l’ln d., 1938, 2 0 , 185— 198).—A lecture, in which industrial processes involving the syntheses of org. substances from C and from H and O (either in the elem entary state or combined as H 20 ) are sum marised, e.g., synthesis of water-gas, MeOH, hydro
carbons, higher alcohols, CH20 , explosives, and
rubber. 0 . J . W .
Cl. III.—ORGANIC INTERMEDIATES. 763 F a tty alco h o ls a n d s u lp h o n a te d fa tty alco h o ls.
M. Co ul er u (Compt. rend. X V II Cong. Chim. Ind., 1937, 722—728).—The applications of the higher aliphatic (oleyl and cetyl) alcohols in pharmacy, lubrication, perfumery, etc., and of the sulphonated alcohols as wetting agents etc., are summarised.
E . L.
P o ly m e ris a tio n of v in y l a c e ta te . L. Me u n ie r
and G. Va is s iJire (Compt. rend., 1938, 2 0 6 , 677—
679).—Polymerisation of commercial vinyl acetate (I) takes longer in air or 0 2 below 120° th an in N 2 because in the former case peroxidation is the first reaction.
Above 120° this peroxide is unstable. Polymerisation by ultra-violet light is similarly inhibited by 0 2.
When (I) is heated w ith an equal vol. of E tO H or E t0 H - H 20 (50—95% of EtO H ) containing 1% of Bz20 2 a t 80° for 3 hr., polymerisation occurs, b u t the polymeride has a low mol. w t. The probable course of the reaction is described. J . L. D.
F o r m a tio n of e s te r s fr o m a lc o h o ls. S. L.
Leltsch uk, M. V . Veltistova, and E. J . Gavrilova
(Prom. Org. Chim., 1938, 5 , 287—292).—The yields of EtOAc or P rC 02Bu obtained when MeCHO or PrCHO is passed in a stream of N2 over Cu-A120 3- Cr20 3 catalyst a t 275° are very small as compared w ith those obtained in presence of H 2 or H 20 , or from E tO H or BuOH. Synthesis of the esters from alco
hols is n o t inhibited b y presence of acids in th e m ix
ture. EtOAc is obtained in good yield from acetal, b u t it is improbable th a t acetal is an interm ediate product. Production of ester under the given con
ditions takes place almost exclusively from acid and alcohol; in the case of aldehydes ester is formed only after reduction to alcohol and oxidation to acid, by H 20 formed or present. D irect condensation of 2 mols. of aldehyde to yield ester does not take place.
R . T.
C a ta ly s ts in tb e p r e p a r a tio n of v in y l e s te r s . M. Je a n n y (Rev. Gen. Mat. Plast., 1937, 13, 203—
205, 267—270).—A review of p aten t literature on the use of salts of Hg, Zn, and Cd as catalysts.
F . McK.
V a p o u r p r e s s u r e of so lv e n ts . D. H. Kil l e f f e r
(Ind. Eng. Chem., 1938, 30, 565—567).—One nomo
graph is given for the v.p.-tem p. relations of 33 common solvents with b.p. between 150° and 200°, and another for 31 with b.p. above 200°. R. C. M.
[ P re p a ra tio n of] m e th y l e th y l k e to n e . V. S.
Batalin and E. V. Sek r etar eva (Sintet. K autschuk, 1936, No. 1, 14—20).—Bu^OH is heated for 2—3 hr.
a t 400—555° (optimum 500°) with calcined (450°;
3—4 hr.) ZnO and the product fractionated to yield 85—88% of COMeEt and 1—3% of unsaturated
hydrocarbons. Ch. Ab s. (c)
In flu en ce of w a te r a n d of o th e r im p u r itie s on c r y s ta llis a tio n of n a p h th a le n e f r o m th e g a se o u s p h a s e . S. S. Urazo vsk i, K. A. Belov, and V. V.
Dib sk i (Ukrain. Chem. J ., 1938, 13, 55—68).—The size of the crystals deposited from C10H 8 vapour diminishes with rising [CeHg], and rises with increas
ing [H20 ] of the vapour. In presence of PhO H the deposit is imperfectly cryst. or amorphous. The effects aro ascribed to surface-energy changes.
R . T.
P r e p a r a tio n of h ig h -g ra d e a n th ra c e n e a n d c a rb a z o le fr o m c ru d e a n th ra c e n e . M. I. Polia kova(Koks i Chim., 1938, No. 2—3, 75— 81).—Crude anthracene is heated for 4 hr. a t 140— 150° with a 115% excess of maleic anhydride (I), the product heated with 10% N a2C 03 or NaOH, and th e solution filtered. The washed residue is shaken with an equal vol. of C6H 6 (1 hr. a t 20°) and filtered, when the residue consists of 70— 77% carbazole, whilst the filtrate yields, when evaporated, 45% phenanthrene. Excess of H 2S 0 4 is added to the alkaline filtrate a t room tem p., and the C6H 6-(I) adduct collected, washed, dried, and heated a t 300° to yield a sublimate of anthracene and (I). The washed sublimate is heated with 10%
NaOH to remove undissociated adduct, and the residue washed, dried, and recryst. from C6H B to
yield 95— 97% anthracene. R . T.
P r e p a r a tio n of p u re a n th ra c e n e a n d c a rb a z o le fr o m p re s s e d c ru d e a n th ra c e n e b y tb e a lk a li- fu sio n m e th o d . I. I. Tz u x e r m a n (Prom. Org.
Chim., 1938, 5, 248—251).—The m ethod described previously (B ., 1937, 1017) gives 80—84% anthracene in 75% yield, and 90—91% carbazole in 60% yield, on a semi-industrial scale. R . T .
P ro d u c tio n of m e to l in th e a u to c la v e . A . E.
Baum an and Z. S. Sc h enk er (Photo-Kino Chem.
Ind. U .S .S .R ., 1935, No. 5,52—56).—p-NH2-C6H 4-OH can be m ethylated in an autoclave by the use of MeOH a t 160— 170°/21—26 atm . (yield 65%).
Ch. Ab s. (e) B y -p ro d u c ts [C 10H 8] fr o m co ke o v ens. 1- a n d 2-C 10H -M e fro m c ru d e o il. M e th y lo c ta n e s fro m p e tro le u m .—See II. C a rb a g e l.—See V II. R u b b e r a n tio x id a n ts .—See XIV. B u ty l- fe rm e n ta tio n .
—See X V III. G ly ce rin fo r p h o to g ra p h ic e m u l
sio n s .—See X X I.
See also A ., II , 214, D e te c tin g M eO H . 215, P r e p , of an h y d . p in a c o l, of d ia c y lo x y -d e riv a tiv e s of k e to n e s, of a c id a n h y d rid e s , a n d of A caO . S y n th e sis of N a 2P h P 0 4. 225, P r e p , of o - ( N 0 2)2- c o m p o u n d s. 228, S y n th e s is of p e ry le n e fr o m a n th ra c e n e . 231, M e th y la tio n of C P h 3-OH. 237, N ew s y n th e s is of m e ta l s a lts of h y d ro x y a n th r a - q u in o n e s. 238, Is o la tio n of g u a ia c o l fro m w a ste s u lp h ite liq u o r. 243, P r e p , of p y rr o lid in e s . 245, Iso la tio n of 2 : 3 -d im e th y l-8 -e th y lq u in o lin e fr o m p e tro le u m . I l l , 525, T o x ic effects of v o la tile so lv e n ts in in d u s try . 534, S u ccin ic a c id .
Pa t e n t s.
P r e p a r a t i o n o f n o r m a l d e f i n e s c o n t a i n i n g A°- a n d A ^ - o le f in e s ( m a i n l y A ^ - o le f m e s ) . A . H . S t e v e n s . From P h i l l i p s P e t r o l e u m Co. (B .P . 482,427, 24.6.36).— A“- and A^-olefines (-i;C4) are prepared-from m ixtures containing also paraffins and tert.-olefines by treating with 80— 100% H 2S 0 4 a t atm . temp, and separating th e acid-ester m ixture before sulphation is complete, tert.-Olefines are poly
merised and Aa- and (chiefly) A0-olefines are regener
ated by diluting the acid-ester m ixture w ith > 100%
of H 20 (to yield 44—65% H 2S 0 4) and heating (85—
150°f. A. H . C.
S ta b ilis a tio n of poly/.s-obutylene. G. W. Jo h n
s o n. F r o m I. G. Fa r b e n i n d. A.-G. (B.P. 482,547 and 482,573, 28.9.36).-— (a) Polymerised mo-C4H 8 is stabilised by adding > 1% of a cyclic amine or phenol.
The use of ^-CH2Ph-NH-CGH 4-OH is described, (b) The use of > 1 % of an org. sulphide, e.g., di-(2-hydr- 0xy-5-butylphenyl) disulphide, is claimed. A. H . C.
M a n u fa c tu re of e tb y l c h lo rid e . G. W Jo h n s o n. From I. G. Fa r b e n i n d. A.-G. (B.P. 483,051, 8.10.36).
—Cl2 and C2H 6 (1— 1-25 mols.) are led over cryst. C (graphite) deposited on m etal carriers. which are resistant to Cl2 and HCl and m ay be cooled, a t 400—700° to yield (70—S0% of) EtCl. A. H . C.
M a n u fa c tu re of p o ly m e ris a tio n p ro d u c ts . I. G.
Fa r b e n i n d. A.-G. (B.P. 482,583, 28.9.36. Ger;, 28.9.35).—U nsaturated substances,: either singly or in mixture, which can be vaporised and are to be poly
merised, e.g., vhiyl halides, are passed in the form of fine gas bubbles up a column of hquid in Which they are insol. and which contains an accelerator in solu
tio n ; unpolymerised gas is recirculated. Among examples, Cfi,*CHCl is passed through a fine nozzle up a tower containing 1% aq. K 2S20 8 a t 50—60°.
The liquid is eventually converted* into a stable emulsion of the polymeride, which is isolated by salt
ing. " K . II. S.
M a n u fa c tu re of p o ly m e ris a tio n p ro d u c ts . W. W. Gr o v e s. F r o m I. G . Fa r b e n i n d. A.-G. (B.P.
482,647, 28.9.36. Cf. B.P. 482,583; p re c e d in g ab - stra ct).-—A g a se o u s, p o ly m e r isa b le org. c o m p o u n d , p a r tic u la r ly a v in y l h a lid e , a lo n e or in a d m ix tu r e w ith o th e r p o ly m e r is a b le g a se o u s c o m p o u n d s, is fin e ly d is tr ib u te d in a liq u id m e d iu m (H20) in w h ic h i t is p r a c tic a lly , in so l. in p r e se n c e o f a p er-co m p o u n d . (IC,S2Oh) a s c a ta ly s t a t > a tm . p ressu re. T h e liq u id m e d iu m m a y a lso c o n ta in so lid or liq u id co m p o u n d s ca p a b le o f b e in g p o ly m e r ise d . R . G.
M a n u fa c tu re of alco h o ls of h ig h m o l. w t.
G. W. Johnson. From I. G. Farbenind. A.-G. (B.P.
482,970, 18.11.36).—H vdroxylated condensation pro
ducts of high mol. wt. suitable for use as textile assist
ants, softejm g agents, synthetic resins, etc. are pre
pared by condensing CHJIelCH-CHO or an aldehyde producing this (e.g., MeCHO, aldol) with compounds having a reactive H and/or a polymerisable double linking in presence of MOAlk (M — alkali metal) and (catalytically) reducing th e product. The use of COMe2, (!CH-C0)20 , cycfohexanone, COMeEt, CH2:CH-C02E t, CH2ICH,COEt; diwobutene, PliOH, and (MeCHO)3 as the second component is described.
A. H. C.
S ta b ilis a tio n of p o ly v in y l e th e r s . G. W . Jo h n
s o n. , From I. G. Fa r b e n i n d. A.-G. (B.P. 482,512, 28.9.36).—Polyvinyl ethers are stabilised before poly
merising by adding > 1 % of a cychc org. amine or a substance containing SI and/or aromatic N H , or OH groups. T he stabilisation of OBu^CELCHl (poly
merised w ith B F3) by di-(2-hydroxy-5-butylphenyl) disulphide and by the analogous Bu^ compound is
described. A. H . C.
M a n u fa c tu re of p o lym e ris a tio n p ro d u c ts . I. G Fa r b e n i n d. A .-G ., a n d W. W. Gr o v e s (B.P. 482,440 a n d B.P. 482,507, [a] 29.9.36, [b] 29.12.36. A d d n s.
to B.P. 459,515; B., 1937, 468).—(a) Polyvinyl ketones are treated with alkaline condensing agents (NH3, org. amines, N H 4 compounds) and the reaction is stopped by adding an equiv. am ount of acid when the desired r, has been attained, the products being still sol. (b) Polymeric compounds, other th an poly
vinyl ketones, containing CO groups, and if desired C 02H in addition to CO groups, and treated as in (a).
Examples describe the treatm en t of products from CH2:CH-COMe w ith CH2:CH-C02Me or CH/.CH-OAc and from styrene, CH?;CHvCHO, and CH2;CH-OAc.
R. G.
P r e p a r a tio n of fS-2> -h yd roxy p b en y l/so p ro p y l- m e th y la m in e . Kn o l l A.-G. Ch e m. Fa b r. (B.P.
482,414, 26.5.37. Ger., 26.5.36 and 18.5.37).—p- OMe-C0H 4vCH2'COMe is condensed w ith N H 2Me, the product either simultaneously or subsequently re
duced, and th e OMe hydrolysed (e.g., with HBr).
N H 2Me m ay be replaced by N H 3 and the base m ethyl
ated (e.g., w ith CH20 and activated Al in EtO H ).
Examples describe th e use of P t- H 2, N i-H 2, and activated Al in E tO H and in H,,0 to effect reduction.
" A. H . C.
M a n u fa c tu re of h y d ro a ro m a tic n itr o g e n c o m p o u n d s . W. J. Te n n a n t. . From He n k e l & Co.
G .m.b.H . (B.P. 482,5S0, 28.8.36).—S aturated hydro
arom atic compounds containing a t least one ahphatic hydrocarbon radical of ■£- C4;and containing reactive Cl, OH, or CO are caused to interact with N H 3 or prim ary or sec. amines, if necessary in presence of H 2.
Among examples, 2-methyl-4:-sec.-dodecylcyclohexan- one, b.p. 162— 168°/2 mm. (280); (formed by interaction of dodecene and o-cresol followed by hydrogenation and oxidation), is heated w ith CH2P h 'N H , (107) and H C 02H (138 pts.) a t 100—150°, producing 2-melhyl- A-seo.-dodecyloyclohexylbenzylamine, b.p. 200—
230°/l mm. Similarly n-octene and PhO H afford 4-sec.-octylq/cfohenanone, which with N H 2Mo in aq. MeOH with N i-H 2 a t 30 atm . for 20 hr. produces A-sec.-octylcyclokexylmethylamine, b.p. 170—175°/14 m m .; 2-methyl-4;-sec.-octylcyclohexylniethylamine, b.p.
148—457°,: is obtained similarly. K . H . S.
M a n u fa c tu re of a r o m a tic p o ly su lp h o n a m id o - c o m p o u n d s. I . G. Fa r b e n i n d. A>G. (B.P. 482,524, 3.10.36. Ger., 5. and 12.10.35).—Products of val.
as tanning agents, reserving agents for wool against substantive dyes, or precipitants for basic dyes are prepared by interaction of an arom atic disulphonic or dicaboxyhc acid halide, an aliphatic dicarboxylic acid halide, or C0C12 w ith an aminosulphonic acid (2 mols.) in which < 2 aryl residues are linked to gether by C O N H and/or S 0 2-NH, and in which there m ay also be present readily hydrolysable (aliphatic) NHAc, N 0 2, or additional N H 2, this free or developed N H 2 being'’finally condensed w ith an aryl-sidphonyl or -carboxyl halide; th e final products have -fc4 SOa-NH, < 5 aryl nuclei, and < 2 S 0 3H . E.g., p-N H 2-CGH 4-SO:)N a is condensed with m-
NOa'Cg^'SOoCi (I) in presence of CaC03, the product is reduced (Fe), condensed with further (I) (1 mol.), again reduced, and finally condensed with 1 : 2- dichlorobenzene-4 : G-disuljihonyl chloride, m.p. 110—
111° (o-CgH 4C12 and excess of C1S03H) (0-5 mol.);
the resulting product is converted into N H 4 salt
Cl. V.—FIBRES; TEXTILES; CELLULOSE; PAPER, 765 which is extremely sol. in H 20 and in presence of
acids is a tanning agent. H. A. P.
M a n u fa c tu re of c o n d e n s a tio n p r o d u c ts co n ta in in g n itro g e n a n d s u lp h u r. W. W. Gr o v e s. From I. G. Fa r b e n i n d. A.-G. (B.P. 482,515,30.9.36).—
“ Sulpho-betaines ” arc prepared by interaction of a m etal salt of an aliphatic halogenosulphonic acid with a tert. am ine; reaction is said to be favoured by H 20 if th e product has H 20 of crystallisation. E.g., the inner anhydride, m.p. 249—250°, of (J-pyridin- iumethanesulplionic acid is prepared by heating Cl-[CH,]2-S03N a (I) with C5H 5N a t 140— 150°.
Similar products are obtained from (I) and N E t3, and from CH2Cl-CH(0H)-CH2-S03Na and quinoline (m.p.
318°), and N E t2-[CH2]2-OH (m.p. 189—190°).
H. A. P.
a n d C a(O H )2.—Sec II . L e u c o -co m p o u n d s.
—Sco IV. T e x tile a s s is ta n ts .—See VI. C a ta ly tic c o m p o sitio n .—See V II. S u lp h o n ic ac id a m id e c o m p o u n d s.—See X X .
IV .-D Y E S T U F F S .
O x id a tio n in th e d y e stu ffs in d u s tr y . F . He n e-
s e y (J. Soc. Dyers and Col., 1937, 53, 345—347).—
The use of various agents in oxidising leuco-com
pounds, particularly of the CHPh3 series, is discussed with special reference to the effect on shade and yield.
Comparison is made between oxidation w ith AcOH-f- PbO , (I), dichromate-f-H2C20 4 (II), and H2C2044- dichrom ate (III) mixtures, the reagents being added in the order given. In the case of Disulphine Green B, (I) is superior to (II) and (III). However, with leuco-Acid Green G, this difference is not so pronounced, although both (II) and (III) give bluer shades [(III)> (II)]. W ith leuco-Disulphine Blue V, all three reagents give good yields, b u t with leuco- Disulphine Blue A, (II) and (III) give very poor yields and green, dull shades. Freshly prepared M n02 is b etter th an K M n04 in some cases (e.g., in the oxidation of the compound produced by condensing o-C6H 4Cl-CHO with o-C6H4Me-NHEt), and in a process involving two stages of oxidation (e.g., in the prep, of Milling Blue B) sufficient reagent (K2Cr20 7) to effect both oxidations m ay sometimes be added. During tho air-blowing of indoxyl, the H 20 2 formed (especially a t low tem p.) produces some o-NH2-CcH4,C 02H and decreases the yield of indigo.
This effect is min. a t 70°. R. J . W. R.
See also A., I, 307, B e h a v io u r of dyes to w a r d s clay e tc . II , 229, C o n g o -re d s y n th e s is . 243, D yes fr o m ac e n a p h th e n e q u in o n e . G re e n v a t dy es fr o m th io p h e n a n d 3 -s u b s titu te d 4 -h y d ro x y - a n th ra n o ls .
Pa t e n t s.
C o n v ersio n of leuco [a n th ra q u in o n e ] c o m p o u n d s in to t h e ir o x id ise d fo rm . G. Lo r d and G. Re e v e s (B.P. 482,582, 26.9. and 14.10.36).—
Leuco-compounds which do not require the addition of 0 2 for conversion into their oxidised form, e.g., OH- and N H 2-derivatives of anthraquinone, are dehydro
genated by heating with unsaturated org. compounds or compounds capable of reacting as such, e.g., CyE^
COMe2, MeCHO, terpenes, alkylene oxides, (CH2)2NH.
The method is applicable to th e development of vat- dyed textiles. E.g., leuco-1 : 4-diam inoanthraquin- one (60 pts.) is;heated with (CH2)20 (13 pts.) in MeOH (600 pts.) a t 150° for 4 h r . ; 1 : 4-diaminoanthraquin- one and E tO H are formed. H. A. P.
M a n u fa c tu re of dy es of th e p h th a lo c y a n in e s e rie s . G. W. Jo h n s o n. From I. G. Fa r b e n i n d. A.-G. (B.P. 482,387, 13.11.36).—Metal phthalocyan
ines aro prepared by heating o-dinitriles or compounds yielding such nitriles during th e reaction (e.g., o-CN,C6H 4-CO-NH2) in presence of metals or m etal compounds under pressure in presence of an org.
diluent free from N and OH groups, preferably ono of b.p. 80— 150°. Examples aro given of tho prep, of Mg, Zn, Cu, Na, Pb, Ni, Cu, Co, Cr, and Fo phthalo
cyanines in PhMe, PhCl, etc. IIg phthalocyanine, obtained by heating o-CGH 4(CN) 2 an d H gPh2 in xylene a t 230°, is brilhant green in shade. Cu tetraphenyl- phthalocyanine is obtained in a p-inodification (soft and insol. in CfiH 6) by heating 3 : 4-dicyanodiphenyl and CuCl in PhMe a t 190—200° for 8—10 hr.
S. C.
S e n s itis in g e m u ls io n s . P o ly m e th in e d y es.—
See X X I.
V .—FIBRES; T E X T ILE S ; C E LL U LO S E ; PAPER.
S tr e s s - s t r a in c h a r a c te ris tic s of w o o l a s r e la te d to its c h e m ic a l c o n s titu tio n , (a) J . B. Speakm an.
(b) M. H a r r i s and J . A. S ookne (Amer. Dyestuff Rep., 1938, 27, 16S— 171p, 171— 173p).—(a) The conclusions of H arris and Sookno (B., 1938, 264) aro disputed and reference is made to previous and hitherto unpublished researches to prove th a t fibre swolling is of less im portance than tho salt linkings formed from the acid and basio sidc-chains of wool in determining th e physical stability of wool fibres in aq. and acid solutions. I t is affirmed th a t new cross-linkings between th e polypeptide chains are formed by the action of quinone on wool and this (but not swelling) explains the increased resistanco to extension of the treated fibres. Tho statem ent of Harris and Sookno th a t the resistanco to extension of wool fibres in aq. HCI a t p a 1-42— 4-95 is unchanged by saturating the fibres w ith Orange I I is con
tradicted and evidence is given to show th a t the dye particles increase this resistance by clogging the fibre stru ctu re; tho hysteresis between extension and contraction of wool fibres is increased from 53-7%
to 80-4, 71-3, and 73-8% by dyeing with 50% of Solway Green G., Solochromo Black, and Solway Blue Black BS, respectively. D ata showing th e % reduction in work required for 30% extension of fully deaminated fibres in solutions of p a 1-00— 11-77 a t 22-2° prove th a t the resistance to extension is independent of the p a in acid solutions; this agrees with tho salt-linking theory since such linkings are broken by deamination. I t is concluded th a t deamination was incomplete in th e experiments of H arris and Sookne. I t is contended th a t H arris and Sookne’s conclusion th a t swelling is a sufficient cause of the increased ease of fibre extension in aq. solutions of neutral salts (with and w ithout the presenco of an acid) is based on a m isinterpretation of the experi
m ental data, and it is affirmed th a t salt linkings play an im portant part; Aq. solutions of neutral salts (e.g., 0-2M-HgCl2 in OTn-HCI) m ay have a drastic action on a strained (but not unstrained) cystine linking.
(b) A reply. The im portance of fibre swelling is again emphasised. The form ation of now cross
linkings by quinone fails to explain the much easier extension of the treated fibre in alkaline solutions, especially because it is found th a t no quinone is removed from the wool by the alkali. I t is contended th a t simple mechanical hindrance by dyes does not explain th a t extension of dyed fibres in solutions o fy n 1-4-—5-0 requires exactly the same energy as untreated fibres and much less energy a t pa 6-9. I t is affirmed th a t tho ease of oxtension of completely deaminated fibres is n o t independent of the pn in solutions of p a <5-0.
Speakm an’s contention th a t the behaviour of wool fibres in aq. solutions of inert inorg. salts is the same as when exposed to atm . in equilibrium with these solutions is denied, and this is supported b y the fact th a t the enorgies required to extend fibres 30% in aq. 5N-LiBr and -NaCl are 0-82 and 1-22, respectively, although the R .H . of the atm . in equilibrium with these solutions are nearly equal (65 and 78%, respect
ively). H arris adheres to a conclusion (with Mease;
B., 1937, 538) th a t wool forms a sulphamic and not a sulphonic acid when trea ted with 80% H 2S 0 4 although this is disputed by Speakman. A. J . H .
P h o to c h e m ic a l re a c tio n of w ool. M. Ha r r is
and A. L. Sm ith (Amer. Dyestuff Rep., 1938, 27, 175— 178p, and J . Res. N a t. Bur. S tand., 1938, 20, 563—569).—During irradiation of wool (surrounded by dry N2) w ith ultra-violet light from a glass-en
closed C arc (Fadeometer) 5-4% of the to tal S is liberated as H 2S ; in moist N2 this decomp, is increased to 22% . Contrary to the conclusions of King (B.,
closed C arc (Fadeometer) 5-4% of the to tal S is liberated as H 2S ; in moist N2 this decomp, is increased to 22% . Contrary to the conclusions of King (B.,