A p p lic a tio n s of p ro p a n e a n d b u ta n e . J . Le
-f r a n c q (Mom. Soc. Civ. Eng. France, 1937, 90, 828—
844).—Liquefied C4H 10 is now used largely as a domestic fuel in country districts in France. Lique
fied C3H 8 is more suitable for industrial applications, some of which are briefly indicated. A. B. M.
In flu e n ce of h ig h p r e s s u r e s on c r a c k in g [of h y d ro c a rb o n s ]. S. S. Na m e t k in and M. M.
Gerasesiov (J. Appl. Chem. Russ., 1938, 11, 413—
419).—The yields of gaseous and liquid hydrocarbons are unaffected, the am ount of H 2 falls, and tho proportion of saturated to unsaturated hydrocarbons in the liquid product rises, when the pressure during cracking is raised from 50 to 430 atm . R. T.
S o lv e n t re c o v e ry in th e c h e m ic a l in d u s tr y . G. Gen in (Tech. Ind. Chim., 1938, No. 277 bis, 163—
168).—A review. I. C. R.
C o n ta c t p o iso n s in th e h y d ro g e n a tio n of e th y le n e . S. B. An is im o v and V. F . Polozov (J.
A p p l. Chem. Russ., 1938, 11, 297—301).—MoS2 catalyst is inactivated by N H 3 or C5H 5N. HCI lowers the activity of MoS2 or Ni, b u t raises th a t of Cr20 3.
R. T.
C o n d itio n s fo r p u rific a tio n of c o m m e rc ia l iso p ro p y l alco h o l m a d e fr o m c r a c k in g g a s e s . A. G. Pukxrev (Sborn. R abot Lab. In st., 1937, 15, 20— 44).—Cracking gas, containing 40—46% of C3H 6, from a 100 kg./day semi-technical “ Chimgas ” plant in Leningrad was hydrated with 88% H 2S 0 4, hydrolysed, and distilled as an azeotropic m ixture containing 20% of H 20 . Other im purities, e.g., hydrocarbons, BuyOH (1), Pr^20 , and higher alcohols, particularly sec.-BuOH, were also present. Methods of preparing pure Pr^OH (II) from the product were investigated. Hydrocarbons and most of the higher- boiling impurities, which form approx 8-5% of the
product, aro removed by treatm ent with aq. NaCl (d 1*13) and by decantation. (I) is removed by boiling -with dil. H 2S 0 4 in presence of A12(S04)3 as catalyst.
Dehydration is best carried out by distillation with C6H G. The final product is of good purity. The existence of an azeotropic m ixture of (I) and (II), of b.p. 82-3°, was no t confirmed. D. G.
P u rific a tio n of e s te r s fr o m a lc o h o l a n d w a te r . A. L . Lio h t m a n (J. Appl. Chem. Russ., 1938, 11, 328—330).—E taO or EtOAc is shaken for 10 min.
with conc. H 2S 0 4 a t 0° and the m ixture distilled, when the distillate contains no E tO H and only traces of H 20 . I f th e ester has b.p. > S 0° it is extracted from tho acid m ixture with light petroleum, which is then
fractionally distilled. R . T.
Is o la tio n of h ig h e r alco h o ls f r o m s y n th e tic r u b b e r b y -p ro d u c ts . I I I . S tr u c tu r e of th e h e x - en o l. S. M. R iv k in and G. N. S a v in a (J. Appl.
Chem. Russ., 1938,11, 420—422).—The alcohol, b.p.
157—158°, is A^-hexenol. R. T.
P r e p a r a tio n of g ly co ls f r o m th e fra c tio n of b .p . 3 5 —40° of lig h t o il fr o m p y ro ly s is of p e tro le u m p ro d u c ts . K . A. Kr a s u s k i and M. M . Mo v s u m- Za d e (J. Gen. Chem. Russ., 1937, 7, 2909—2912).—
The fraction of b.p. 35— 40° is condensed with HOC1, and the chlorohydrin m ixturo converted into oxides by K rasuski’s m ethod (cf. A., 1907, i, 459, 999). The oxides yield a m ixture of glycols, chiefly OH-CHMe-CHEt’OH and OH-CHMc-CMe2*OH,whence it is concluded th a t the m ost im portant constituents of th e fraction are CHMelCHEt and CHMeiCMe,.
"R. T.
S y n th e tic a c e tic a c id . Wo l f f (Tech. Ind. Chim., 1938, No. 277 bis, 49—52).—Production from MeCHO, C»H2, E tO H , CO + MeOH, and keten is discussed.
I. C. R.
H is to ry a n d c h e m is try [th e o ry ] of la rg e -s c a le fa tty a c id s y n th e s is . A. Im h a u s e n (Chem.-Ztg., 1938, 62, 213—215).—A lecture on th e formation of fa tty acids by th e oxidation of hydrocarbons produced by the Fischer-Tropsch synthesis from water-gas.
E. L.
P r o d u c tio n of fo rm a ld e h y d e b y o x id a tio n of g a se o u s p ro d u c ts of p y ro ly s is a n d c r a c k in g . II . M. M . Tic h o m ir o v a and V. Mo n a c h o v a (Azer. Neft.
Choz., 1935, No. 6, 79—83; cf. B., 1936, 631).—Tho oxidation was . carried out w ith a h a t 280—340°, using a V20 5 catalyst pptd. on asbestos, refractory clay, or kaolin. The product contained 5— 11% of CBUO, 2 -3 - 5 % of H C 02H , and 6—7% o f AcOH.
Traces of E tC 0 2H were found in the oxidation products from C2H 4 and C3H G fractions; th e amounts from C3H 6-C4H 8 fractions were considerably larger.
The kaolin carrier was best. Ch. Ab s. (e) E tb a n o la m in e s . J . Wa k e l i n (T e x t. C ol., 1938, 60, 373—375).—T h e ir m a n u fa c tu r e a n d u s e in t e x t ile w e t-p r o c e ss in g are d e sc r ib e d . A. J . H .
C h lo rin a tio n of b e n z e n e . I I I . “ O x id a tiv e "
m e th o d , u s in g h y d ro g e n c h lo r id e - a ir m ix tu r e s . N. N. V o r o s h c o v , I. S. T r a v i o n , and 1 .1 . J o f f e (J . Appl. Chem. Russ., 1938, 11, 271—285; cf. B., 1935, 1036).—C6H g, HCl, and 0 2 are passed over CuCl2- FeCl3-S i0 2 srel a t 300°, to yield PhCl and a m ixture of
polychlorides; th e relative yield of the latter rises with rising temp, and increasing [HCl] of th e m ixture, b u t is independent of th e flow velocity. A Cu0-A120 3- F e20 3 catalyst gives max. yields of PhCl a t 2 0 0 °, with exclusively CGH 4C12 as by-product. The relative yields of C6H 4C12 rise to a limiting val. w ith increasing tim e of service of th e catalyst. R . T.
P ro d u c tio n of c o n c e n tra te d a n th ra c e n e b y s u lp h o n a tin g c ru d e a n th ra c e n e in a n in d iffe re n t so lv e n t, a n d u tilis in g th e s u lp h o n a te d p ro d u c t fo r s y n th e tic ta n n in g a g e n ts . J . P. Ber icm anand D. V. To l k a t s c h e v (Trans. V I Mendeldev Congr., 1935, 2, P t. 1, 963—972).—Material containing 10—
15% of anthracene (I) and 15—25% of carbazolo is treated with conc. H 2S 0 4 in kerosene fo r 2£ hr. a t 90—100° to yield a conc. (60%) (I), a sulphonation product which can be incorporated with crude (I) and CjoHg to furnish a tanning agent, and crude phen-
antlirene. Ch. Abs. (c)
In flu e n ce of iro n , c o p p e r, a lu m in iim i, n ic k e l, s ilv e r, a n d m e r c u r y s u lp h a te s , a n d of v a n a d iu m p e n to x id e , on s u lp h o n a tio n of a -n a p h th y la m in e . V. A. Le n c h o l d and E. A. Sa f b o n e n k o (J. Appl.
Chem. Russ., 1938,11,286—296).—The rate of elimin
ation of H 20 from a-C10H 7-NH2,H2S 0 4 a t 145-—200°
is practically the same in presence of the sulphates, or o f V20 6, as in th e h absence, and the relative yields of 1 : 2- and 1 : 5-isomerides do n o t vary significantly.
R . T.
A p p lic a tio n s of e s te r s of j>-hydroxybenzoic a c id a s p re s e rv a tiv e s . T. Sa b a l it s c h k a (Siiddeuts.
Apoth.-Ztg., 1 938, 78, 2 9 — 3 1, 37— 4 0 ; cf. B., 1937, 9 7 7 ).—As bactericides the esters are much less toxic th a n and much more powerful th an is BzOH and have no detrim ental effects on hum an beings. They are used for preserving food, H 20 , drugs, and biological
m aterials. W . McC.
N a p h th e n ic a c id s [a n d t h e i r a p p lic a tio n s ].
V. E. Pa k c iio m e n k o (Neft, 19 3 2 , 3 , No. 7, 14—16).— A review of methods of separating naphthenic acids.
T heh applications in th e soap and varnish industries
are discussed. Ch. Ab s. (ej
R e fin in g of s y n th e tic [n a p h th e n ic ] a c id s . V . Va r l a m o v and Z. Ke n ig s b e u g (Maslob. Shh. Delo, 1 9 3 5 ,11, 2 0 3 ).—Rabinovitsch and Osonova’s m ethod (B., 1937, 876) is modified by treating oxidised petro
latum with 4 pts. by w t. of naph tha (b.p. 75—115°), washing with 6-5% of 93—98% H 2S 0 4, and bleaching w ith 5% of active clay. Ch. Ab s. (e)
Im p ro v in g th e c o lo u r of a c id o l [n a p h th e n ic a c id s a lts ]. D. Go l d b e r g and M. Kotzo ev a
(Maslob. Shh. Delo, 1 9 3 5 ,11, 5 9 4 — 5 9 6 ; cf. B., 1 9 3 7 , 8 7 6 ).—T reatm ent of acidol, w ith and w ithout benzine, w ith H 2S 0 4 of various concns. gave no decolorisation.
Vac! distillation with steam improved the colour, b u t th e product was contam inated with Fe and required further purification w ith H 2S 0 4. The best results were obtained with activated C, b u t this retained considerable acidol. Ch. Ab s. (e)
T h e o ry of r e p e a te d s u lp h o n a tio n of n a p h th e n ic a c id s . E. L . Le d e r e r (Petroleum, 1 9 3 8 ,3 4 , No. 19, 12).—I f p 0 is the % of sulphonatable acids originally present in th e m aterial and. p n tho % of sulphonated
C l. I I I . —ORGANIC INTERM ED IATES. 885 acids after n sulphonations (carried out under the
same conditions) th e following relation is derived : log p n = a + 6/2", where a = log p and b = log {pol'pn )• Tho formula gives results agreeing with those obtained experimentally by von P ilat (B., 1938,
438). A. B. M.
S u lp h o n a tio n of n a p h th e n ic a c id s . W. Ki s i e l e-
w ic z, S. Pi l a t, and J . Se r e d a (Ole, F ette, Wachse, 1938, No. 3—4, 15—18; cf. B., 1938, 483).
S y n th e s is of v a n illin a n d o th e r h y d ro x y - a ld e h y d e s. N. I. Vo l i n k i n (J. Appl. Chem. Russ., 1938, 11, 423—425).—Vanillin is obtained in 76%
yield from guaiacol 5, 40% CH20 solution 3-6, E tO H 20, 30% HCI 25, ^-NO'C0H 4'NMe2 6, and Al powder
0-9 g. (4 hr. a t 38—40°). R . T.
C a ta ly tic o x id a tio n of b o rn y l c h lo rid e . B. N.
Ru t o v s k i, I. P . Lo s e v, and E. V. Me sc h etsc jik o (J.
Appl. Chem. Russ., 1938,11, 311—315).—Max. yields of 42% of campbenc were obtained by passing bornyl chloride-H20 -a ir m ixtures overV 2Os-pum ice catalyst a t 150°; a t higher tem p, tho am ount of HCI eliminated rises b u t tho yield o f camphene falls. Under analogous conditions camphene is recovered u n
changed. R. T.
D is tilla tio n a n d re c tific a tio n .—See I. S y n th e s e s fr o m co k e -o v en g a s . A b s o rb e n t fo r C S2 re m o v a l. R e m o v in g C 10H 8 fr o m w a te r-g a s . C o rro sio n b y su lp h o n ic a c id s . P h e n o ls fro m t a r - H aO . C 3H 8, C 4H 10, e tc . P o ly m e ris a tio n of b u te n e s . S y n th e tic a c id s fr o m p e tro le u m p r o d u c ts .—See II. G u a ia co l a n d p y ro g a llo l 1 : 3 -M e2 e th e r f r o m w a s te p u lp liq u o r.—See V. [A ppli
c a tio n s of] N i c a ta ly s ts .—See X . A n a ly sis of g ly c e ro l.— See X II. U tilis in g a g r ic u ltu r a l w a s te p ro d u c ts .—See XVI. D e te rm in in g g ly c e ro l in w in e .—See X V III. D e te c tin g fu rfu ra ld e h y d e in h o ney. F o o d fla v o u rs .—See X IX . n- N H 2-C6H 4- S 0 2-NH2.—See X X .
See also A., I, 365, E le c tro c h e m ic a l “ n i tr a t io n .”
II, 257, P r e p , of e s te r s , a n d of a -c h lo ro c ro to n ic a c id . 258, P r o d u c tio n of m a le ic a c id . 272, P r e p , of s u lp h o n a m id e s of N H 2P h , a-C 10H 7\N H 2, a n d th e to lu id in e s . 285, P r e p , of b e n z o y lfo rm a m id e . 291, E le c tro -re d u c tio n of A7-p h e n y ls u c c in im id e . 293, P r e p , of 4 -a ry la m in o -2 -a ry lq u in o lin e s . I l l , 607, CC14 p o iso n in g .
Pa t e n t s.
(a , d , E) D e h y d ro g e n a tio n , (b, c ) co n v e rsio n , of a lip h a tic h y d ro c a rb o n s . U n i v e r s a l O i l P r o d u c t s Co. (B.P. 483,184—5, 483,189, 483,190, 483,192, [a ] 30.3., [b] 5.4., [c, d ] 21.4., [e ] 30.4.37. U.S., [a ] 17.9.,
[b, c] 30.9., [d , e ] 15.10.36).—(a ) S aturated aliphatic hydrocarbons containing < C 6 in linear arrangement (I) and freed from II20 are dehydrogenated to mono- olefines (II) a t 450—650°/I atm . by passing over catalysts for 0-5—7 sec. Similarly (I) m ay be con
verted directly into diolefines (III) a t 500—700°/<1 atm . for 0-1—2 sec. and (II) into (III) a t 500—700°/
0-25 atm . The catalysts (pellets or granules, 1*6—12- mesh/cm.) consist of A120 3, MgO, bauxite, or clays impregnated with 1—10% of an oxide of Ti, Zr, Ce, Hf, or Th. The dehvdrogenation of C4 and C5 hydro
carbons (formation of isoprene etc.) is described, (b) The passage of saturated or mono-olefinio hydro
carbons < C B over catalysts consisting of < 1 0 % of an oxide of V, Nb, or T a on a carrier as in ( a ) a t 400—
700°/0-25— 7 atm . for 6— 50 sec. yields arom atic hydrocarbons in good yield. The dehydrogenation of m-C6H 14, m-C7H 16, and corresponding olefines to CeI I 6 and PhMe is described, (c) Catalysts containing oxides of Cr, Mo, W, or U on carriers are also effective as in ( b ) . (d ) Hydrocarbons as in ( a ) are dehydro
genated to (II) and (III) using catalysts as in (c).
(e) Dehydrogenation of hydrocarbons as in (a) is also effected by the catalysts claimed in (b) . A. H . C.
P ro d u c tio n of c a rb o n te tra c h lo rid e . W. J.
Te n n a n t. From D o w Ch e m. C o. (B.P. 484,888, 23.11.37).—Pure CC14 is produced by th e interaction of CS2 and excess o f a S chloride (SC12) a t 40— 150°/
1-5— 10 atm . and distilling the product a t < 1-5 atm .
Apparatus is described. A. H . C.
M a n u fa c tu re of [o rg a n ic ] h a lo g e n a tio n p r o d u c ts . W. W. G r o v e s . From I. G. F a r b e n i n d . A.-G. (B.P. 483,823, 25.9.36).—Halogen vapour is blown through a capillary tube into a vertical tube in countercurrent to a liquid org. compound which m ay contain a catalyst. Examples aro the chlorin
ation of C6H 6, m-C5H 12, CJycZoliexane, AcOH, and petroleum and the brom ination of AcOH in presence of F e d , or S,C1,; apparatus is described.
3 2 A .H . C.
P o ly m e ris a tio n of o lefines. St a n d a r d Oil
De v e l o p m e n t Co. (B.P. 484,170, 31.10.36. U .S ., 30.12.35).—In the polymerisation of olefines for use as m otor fuels the ^-constituents are first polymerised over catalysts a t >200° (200—350°) and the residual gas, enriched in isoolefines, th en polymerised a t > 150°
(50—150°) to yield products of improved antiknock val. Oxides of Al, La, P, or A1C13, CdCl2, etc., either alono or on carriers, are catalysts. A pparatus is described and th e treatm ent of C4H 8 m ixtures is
claimed. A. H. C.
M a n u fa c tu re of b u ta d ie n e . R. Hil l, E. Is a a c s, and Im p e r ia l Ch e m. In d u s t r i e s, Lt d. (B.P. 483,989, 28.7.36).—(CH2:CH)2 is prepared in good yield by heating monocarboxylic esters of (0H-CHMe)2 a t 475—600°. The use of th e diacetate is claimed and th a t of th e diformate is also described. A. H . C.
P ro d u c tio n of p o ly m e rid e s of h ig h m o l. w t.
St a n d a r d Oil De v e l o p m e n t Co. (B.P. 483,453, 7.9.37. U .S ., 10.10.36).—Polymerides of olefines (e.g., of iso-C4H 8) (mol. wt. 1000—250,000) are prepared by introducing the liquid olefine into a liquid bath of norm ally gaseous hydrocarbon a t
< — 10° containing a halide catalyst (BF3). Tho suspension of polymeride is continuously withdrawn and replaced bv fresh catalvst and solvent.
A. H . C.
M a n u fa c tu re of u n s a tu r a te d h y d ro c a rb o n s . G. W. Jo h n s o n. From I. G. Fa r b e n i n d. A.-G.
(B.P. 484,660 4.11.36 and 22.9.37).—Aliphatic or alicyclic halogenated hydrocarbons ( < C3) are con
verted into unsaturated hydrocarbons by bringing in contact for < 1 sec. w ith an electrically-heated body.
The conversion of C4H 8C12 and C4H 7C1 into (CH2;CH)2
and CjHg and the dehydrohalogenation of C3H 6C)2 in contact with N i-Cr wire or graphite are described.
A. H. C.
P ro d u c tio n of alco h o ls. N. V. d e Ba t a a f s c h e
Pe t r o l e u m Ma a t s., Assees. of G. H. Va n De
Gr ie n d t (B .P . 484,437, 17.6.37. U.S., 17.6.36).—
The absorption products of olefines in H 2S 0 4 are hydrolysed to give alcohols b y heating the acid liquor with H 20 a t about 40—75° in a substantially closed system so as to m aintain an acid concn. of 50—90%
calc, on a hydrocarbon-free basis and under a pressure
> the partial pressure of the absorbed olefine to pre
vent distillation. Olefines m ay be passed into the acid liquor during hydrolysis. Sp. claim is m ade to the conversion of see.-butylene into Bu^OH. R. G.
M a n u fa c tu re of alco h o ls a n d e th e r s . H . Dr e y
f u s (B.P. 485,142, 14.11.36 and 18.9.37).—Alcohols or ethers are obtained by passing an olefine (preferably
< C9), H 20 or an alcohol (including a polyhydric alcohol), and a compound of P (e.g., esters, amides, and anilides of H 3P 0 4 and H 3P 0 3, phosphines, tetraphos- phonium bases, and phosphine oxides) in a disperse phase through a hot reaction zone, preferably a t 250—
300° under pressure. In the examples, C2H 4, H 20 , and 0-25% of PO(OEt)3 a t 280°/15 atm . give EtOH, and C2H 4 or C3H 6 and E tO H in presence of 0-3% of H 3P 0 4 and preferably a N a P 0 3 catalyst give E t20 or
E tO P r. S. C.
C o n c e n tra tio n of aq u e o u s b a lo h y d rin s o lu tio n s . N. V. d e Ba t a a f s c h e Pe t r o l e u m Ma a t s. (B .P . 484,884, 3.11.37. Holl., 17.11.36).—Aq. halohydrins (e.g., those obtained by the action of Cl2 and H 20 on olefines) are conc. w ithout neutralising by introducing them a t a uniform ra te into a distillation apparatus a t a point where the composition of the hquid is sub
stantially identical with th a t introduced. An example describes the concn. of a 10% solution of CH,C1-CH2-0H
to 35—40%. "A. H. C.
C a ta ly tic re d u c tio n of c a rb o x y lic a c id s . G. W.
Jo h n s o n. From I. G. Fa r b e n i n d. A.-G. (B.P.
484,995, 10.11.36).—Mixtures of non-aromatic acids of high mol. wt. (e.g., those obtained by oxidising non- arom atic hydrocarbons), are reduced to alcohols by H , a t 150—350°/100—300 atm . in presence of basic oxides of bi- or ter-valent m etals equiv. to the free acid and of Ni, Co, or Cu. Examples describe the reduction of acids derived from paraffin oil and wax
and Diesel oil. A. H. C.
M a n u fa c tu re of eth y le n e o x id e. Dist il l e r s
Co., Lt d., H. La n g w e l l, and H. M. St a n l e y (B.P.
485,033, 17.2.37. Addn. to B .P. 466,417; B., 1937, 758).—Active C which has become inactive by con
tinued adsorption and desorption of (CH2)20 is revivified by treating with hot H 20 (90° for 24 hr.) or with a solvent sol. in H „0 (EtOH , PrOH), and drying.
A. H . C.
M a n u fa c tu re of o rg a n ic c o n d e n sa tio n p ro d u c ts . E . I. D u Po n t d e Ne m o u r s & Co. ( B .P . 483,828, 26.10.36. U.S., 26.10.35).—Cyclic diethers are pre
pared by interaction of olefines and aldehydes in presence of (mono- to penta-)hydrated B trihalides;
e.g., B F3 (150) and then C3H 6 are passed into 37% aq.
CH20 (172) a t 0—20°/I atm . to give, by subsequently
making alkaline and distilling, cyclic butylene glycol formal, C H M e < ^ ^ > 0 , b.p. 113— 114-3°, and other higher-boiling formals. N. H . H.
S u b s ta n c e s u se fu l a s w e ttin g , w a s h in g , a n d p u rify in g a g e n ts a n d p ro c e s s e s of m a k in g th e s a m e . H. Le d e r e r (B.P. 483,301, 10.8.36).—The substances are obtained by sulphonating hydroxyalkyl polysulphides (< C16). Examples describe th e con
version of 10-chloro-octadecanol into the thiocyanate and thence into octadecanol 10-disulphide, which is treated w ith 20% oleum in CC14, and also the brom ina
tion of “ poppy oil-fat alcohol m ixture,” conversion of th e resulting “ tetrabrom ostearin alcohol ” into the disulphide, and treatm ent w ith C1S03H in CHCL.
A. H. C.
M a n u fa c tu re of o rg a n ic a c id s a n d e s te r s . E. I. D u Po n t d e Ne m o u r s & Co. (B.P. 483,577, 21.10.36. U.S., 22.10.35).—Org. acids and/or esters are prepared by the interaction of CO and aliphatic alcohols in th e liquid phase in presence of catalysts containing B (1 mol.), a halogen, and < 5 mols. of H 20 a t < 3 5 0 ° /l— 1000 atm . (350—900 atm .). The prep, of AcOH and E tC 0 2H in presence of B F3- H 20 is
described. A. H. C.
M a n u fa c tu re of [alky l] e s te r s . H . Dr e y f u s
(B.P. 485,108, 14.11.36).—E sters are obtained by passing an olefine (C2H 4, C3H 6, C4H 8), an org. acid [AcOH, P rC 0 2H, (-CH2-C02H )2], and a compound of P (e.g., esters, amides, and anilides of H 3P 0 4 and H 3P 0 3, phosphines, tetraphosphonium bases, and phosphine oxides) through a hot reaction zone, preferably a t 300—650° and under pressure. In th e example, EtOAc is obtained by passing a m ixture of C2H4 and AcOH containing 0-3% of PO(OEt)3 a t 30 atm . through a baffled tube a t 550°. S. C.
M a n u fa c tu re of a c e ta ld e h y d e fr o m g a s e s co n ta in in g a c ety len e. I. G. Fa r b e n i n d. A.-G., and G. W. Jo h n s o n (B.P. 484,500, 25.11.36. Addn. to B.P. 460,145; B., 1937, 326).—Unpurified electric arc gases containing small am ounts of C2H 2 are introduced in a finely dispersed state (through a nozzle) into a catalytic iiquid containing Fe and Hg sulphates as in the chief patent, b u t in absence of filler or contact bodies. A pparatus is described. A. H. C.
C h lo rin a tio n o r b ro m in a tio n of k e to n e s . I. G.
Fa r b e n i n d. A.-G. (B.P. 484,409, 4.11.36. Ger., 5.11.35).— a-Halogeno-ketones are prepared by inject
ing the halogen through narrow tubes in counter- current to the ketone vapour a t a tem p. < th e b.p.
of the halogenated product so th a t the latter is a t once removed from the reaction zone whilst unattacked ketone is recirculated. The chlorination of COMe2, COMeEt.and C O PA , and the bromination of COPhMe,
are described. A. II. C.
P r o d u c tio n of m e th y lo lu re a in s o lu tio n o r c ry s ta llin e fo rm . N . Lu b ic z(B.P. 484,209,2.11.30).
—Urea is condensed w ith 2 or < 2 mols. of CH20 in presence of sufficient of an ethanolamine to keep the solution neutral or alkaline to yield di- or mixtures of mono- and di-hydroxymethylureas. T reatm ent of fabrics with the ureas or with the products obtained
Cl. I I I . —ORGANIC INTERM ED IATES. 887
"by further condensation by heat-treatm ent is also
claimed. A. H . C.
S e p a r a tio n of n itrile -h y d ro c a rb o n m ix tu r e s . Ar m o u r & Co. (B.P. 4 8 4 ,3 5 2 , 1 0 .4 .3 7 . U .S ., 2 4 .9 .3 6 ).
— M ix tu res o f a lip h a tic n itr ile s a n d h y d ro ca rb o n s, w h ic h m a y b e o b ta in e d b y p y r o lisin g n itr ile s C12_18, a re se p a r a te d b y p r e fe r e n tia lly a d so rb in g t h e form er o n a c o lu m n o f S i 0 2 g e l, a c tiv a te d C, A120 3, fu lle r ’s e a r th , or n a tu r a l silic a te s, a n d r e c o v e r in g th e n itrile, e.g., b y d is tilla tio n , fro m th e a d so r b e n t. A . H . C.
M a n u fa c tu re of u re th a n e s c o n ta in in g c a rb o x y l o r su lp h o n ic a c id g ro u p s . I . G. Fa r b e n i n d. A.-G.
(B.P. 484,683, 9.11.36. Ger., 8.11.35).—Urethanes R-0-C 0-N (R')-R "X (R = abietinyl, R ' = H or org.
radical, R " = org. radical, and X = a t least one C 02H, SOjH, or sulphuric ester group) are prepared by interaction of aliphatic, cycZoaliphatic, or aromatic amino-carboxylic or -sulphonic acids or sulphuric esters of amines or substitution products thereof containing a t least one II attached to N, with chloro- carbonic esters of abietinols (abietinol, di- and tetra- hydroabietinol, or substitution products), if desired in presence of dispersing agents. The products possess adhesive properties and are suitable as assistants in the textile and related industries. R. G.
M a n u fa c tu re of u n s a tu r a te d [a ro m a tic ] h y d ro c a rb o n s . G. W. Jo h n s o n. From I. G. Fa r b e n i n d. A.-G. (B.P. 4 8 4 ,5 2 5 , 2 0 .2 .3 7 . Addn. to B.P. 4 7 0 ,2 5 8 ; B., 1937, 1169).—Aromatic hydrocarbons, b.p. <300°, with saturated or unsaturated aliphatic side-chains, are subjected to the process of the chief p a te n t; e.g., P h E t is converted into CPhuCH. R. G.
P u rific a tio n of h a lo g e n a te d a r o m a tic h y d ro c a rb o n s . Br it. Th o m s o n-Ho u s t o nCo., Lt d. (B .P . 483,202, 29.7.37. U.S., 31.7.36).—Halogenated mix
tures (e.g., halogenated P h 2 used as an electrical insulator) arc freed from suspended or colloidal C by agitating, preferably a t 50—80°, with (25% of) an aq. solution producing m ultivalent cations (3%
CuS04), either alone or with additional base (3%
NaOH), C being removed in the aq. layer or on the
m etal hydroxide. A. H. C.
M a n u fa c tu re of ca rb o cy c lic b a s ic p ro d u c ts . W. W. Gr o v e s. From I. G. Fa r b e n i n d. A .-G . (B.P.
484,906, 7.10.36).—Carbocyclic compounds containing N, useful as foaming, wetting, etc. agents, and as insecticides and fungicides, are prepared by the interaction, if desired in presence of a diluent and a catalyst (Cu), of an aliphatic halogeno-ether of an aromatic or hydroarom atic compound substituted by a t least one saturated aliphatic or carbocyclic hydro
carbon radical of < C3, and in which the aliphatic halogeno-ether radicals contain a t least C2 and the a-C is free from halogen, with NH3 or a primary, sec., or tert. amine. The. starting m aterials are prepared, e.g., by the interaction of a suitable aromatic or hydroarom atic OH-compound with an alkylene oxide or chlorohydrin and treatm ent of th e product with a H halide, SOCl2, or CH20 and HCI. The products m ay be rendered sol. in H 20 by, e.g., sulphonation or alkylation. An example is the product from iso- dodecylplienyldecaethylene gtycol and SOCl2 (728) with NH2Me (125) and MeOH (375 pts.) a t 140—
160°/pressure for 6 hr., which after heating with diglyeollic anhydride is a cleansing agent. N. H . H.
M a n u fa c tu re of a c id a m id e s . W. J . Te n n a n t. From He n k e l & Co. G .m.b.H . (B.P. 484,910, 9.11.36).
—Carboxylic amides, useful as washing, emulsifying, wetting, etc. agents, are prepared by the interaction of hydroarom atic prim ary or sec. amines containing a t least one aliphatic hydrocarbon chain of < C4 with carboxylic acids or their derivatives. Suitable car
boxylic acids (or their anhydrides or halides) are AcOH, BzOH, stearic acid, H ^ O ^ o-C6H4(C02H )2, C 02H-C6H4-S03H, SH-CH,-C02H, halogenocarb- oxylic acids, CHPh;CH-COaH, and oleic acid. H ydro
phile groups m ay be introduced into th e amides by after-treatm ent with, e.g., alkylene oxides, sulphonat- ing agents, alkylating agents (to give, when N H 2 is present, quaternary salts). Examples are th e tre a t
m ent of 4-sec.-octylc?/cfohexylaniine, b.p. 110— 130°/2 mm., with 0Ph-CH2-C02H, tolyloxyacetic acid, or succinic acid to give the corresponding amide, and the after-treatm ent of the first-named two with conc.
H 2S 0 4 to give sol. wetting agents. N. H. H.
M a n u fa c tu re of b a sic s u b s titu te d c a rb o x y lic a c id a m id e s . De u t s. Hy d r i e r w e r k e A.-G. (B.P.
483,324, 16.10.36. Ger., 16.10.35).—These amides are prepared by interaction of carboxylic acids (I) containing quaternary N H 4 groups or intramol.
483,324, 16.10.36. Ger., 16.10.35).—These amides are prepared by interaction of carboxylic acids (I) containing quaternary N H 4 groups or intramol.