M a n u fa c tu re of b u ta d ie n e . I . G. Fa r b e n i n d.
A.-G. (B.P. 486,264, 21.7.37. Ger., 24.7.36).—
(CH2:CH)2 is m ade by heating (150—240°) butylene glycol with an org. sulphonic acid free from mineral acid, continuously fractionating th e products, remov
ing gaseous (CH2!CH)2, and separating th e liquid distillate into an aq. layer and an org. layer of interm ediate products which is returned to the still.
The use of C10H 7-SO3H is described. A. H . C.
[M a n u fa c tu re of] b u ta d ie n e s a n d c h lo rin a te d d e riv a tiv e s th e re o f. I. E. Mu s k a t, Assr. to E. I.
D u Po n t d e Ne m o u r s & Co. (U.S.P. 2,070,609, 16.2,37. Appl., 14.7.34).—BuCl is chlorinated to C4H 8C12, the product fractionally distilled, and the individual fractions, particularly ay-C4H 8Cl2, are passed over an alkaline agent (soda-lime) a t 700— 730°
or flash-distilled in presence of similar agents to yield
(CH2:CH)2. A. H. C.
M a n u fa c tu re of p r o d u c ts of h ig h m o l. w t.
so lu b le in m in e r a l o ils. 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. 486,161, 22.3.37. Holl., 24.3.36).—Products of mol. wt. >1500 which are sol.
in and improve the rL of mineral oils are prepared by condensing iso-C4H 8 or -C5H 10 with compounds con
taining a t least one halogen atom and a t least one double linking (e.g., chloroprene) in presence of a catalyst ( B F 3) a t < 0 °. A. H . C.
P r o d u c tio n of p o ly m e ris a tio n p r o d u c ts of t e r t i a r y o lefm es. 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 F . A. Be n t, R. W . Mi l l a r,
and S. N. W ik (B.P. 487,166, 15.12.36. U.S., 23.12.35).—Polymerisation products for use in the prep, of fuels of high antiknock val. are obtained by bringing a tert.-olefine (I), which may be mixed with paraffins or other olefines, in contact with aq. mineral acid (H2S 0 4) of < 5 0 % concn., preferably 0-5— 45%
(1—25%), a t <100° (<125°) and a t such pressure ( > atm .) th a t substantial conversion of (I) into dimcride takes place a t a practical rate. H 20 may be added with (I) to m aintain the vol. of the aq. acid a t 150—350°, and the reaction products are removed a t such a rate th a t (I) is substantially converted into dimeride. Sp. claim is made to the treatm en t of CH,:CMe„ with aq. 3— 10% H 2S 0 4 a t 150—250°.
R. G.
T r e a tm e n t of u n s a tu r a te d h a lid e s . M. W.
Ta m e l e and H. P. A. Gr o l l, Assrs. to Sh e l l De v e l o p m e n t Co. (U.S.P. 2,072,015, 23.2.37. Appl., 4.10.32).—U nsaturated halides of the allyl type (< C 4) which m ay contain a tert. C are converted into alcohols by heating for >1 hr. with aq. alkali or alkaline-earth hydroxide a t 80—250° under pressure. The con
version of CH2Cl-CMe!CH2 into the alcohol and its separation from isomeric chlorides (e.g., of the vinyl type) by preferential hydrolysis is claimed, and batch and continuous processes for similar hydrolyses and ammonolyses (e.g., of chlorinated C4H 8 and C5H 10)
are described. A. H. C.
M a n u fa c tu re of p o ly m e ric p ro d u c ts of a c e ty l
e n e . W. W. Gr o v e s. From I . G . Fa r b e n i n d.
A.-G. (B.P. 486,918, 5.12.36).—C2H 2 is polymerised to vinyl- and divinyl-acetylene by passage, preferably a t 90— 100°, through liquid contact substances con
sisting of low-melting complex salts of Cu1 and a salt of N H 3 or an aliphatic, hydroarom atic, or heterocyclic base, e.g., th e salt, N H 2Me,HCI,CuCl, m.p. 80°; equal wts. of N H 2Me,HCl and CuCl; 1 p t. of CuCl and 0-53 p t. of N H 4C1, m.p. 140°; equal wts. of CuCl and C5H 1;lN ; equal parts of NHMe2,HCl, NMe3,HCl, and 0H-[CH,]„-NH„HC1 and 2-5 pts. of CuCl, m.p. <30°.
S. C.
H y d ra tio n of o lefin es. E . I. D u P o n t d e Ne m o u r s & Co. (B.P. 486,783, 9.12.36. U.S., 13.12.35).—Olefines are hydrated in th e liquid or vapour phase to ethers and alcohols in presence of a B-halogcn compound (BF3) a t 125—300° (175—
225°)/25—900 atm . The continuous hydration of C2H 4 and C3H 6 is described. A. H. C.
P r o d u c tio n of alco h o ls [by re d u c tio n of fa tty a c id s a n d t b e i r e s te r s ] . C. 0 . He n k e and R. G.
Be n n e r, Assrs. to E. I. D u Po n t d e Ne m o u r s &
Co. (U.S.P. 2,070,597, 16.2.37. Appl., 14.11.34).—
F a tty acids (C6_ 22), their esters, or glycerides are reduced w ith an alkali m etal (Na) and a cycloaliphatic alcohol (hydrogenated cresols). E.g., coconut or sperm oil is trea ted with Na an d hydrogenated cresylic acid in xylene a t 105— 115°. H . A. P .
P r o d u c tio n of a lip h a tic alco h o ls a n d e th e r s .
Ca r b i d e a n d Ca r b o n Ch e m i c a l s Co r p., Assees. of J . F . Ev e r s o l e and C . W. Re h m (B.P. 487,384, 17.12.36. U.S., 24.12.35).—Olefines and ethers are hydrated a t high temp, and pressure in presence of a catalyst comprising essentially a heteropoly-acid (I) and/or salt thereof or an isopoly-acid (II) of high mol. wt. (I) comprises a nuclear element (P, Si, B, As) surrounded preferably by 12 co-ordinated groups of oxides of W , Mo, V , Cr, S, Se, or Te, particularly silico-, boro-, phospho-, phosphomolybdo-tungstic, phosphomolybdic, or tungstoarsenic a c id ; (II) are complex acids of W, Mo, V, or Cr. Salts which may be used are those of Th, Al, W, Cr, Cd, Ag, Cs, Hg*, or alkali metals. The catalyst m ay be used in solid form suspended in a non-reactive medium or deposited on an inert carrier (Si02 gel, C, etc.). Sp. claim is made to th e passage of a gaseous m ixture of H 20 and a hydrocarbon m ixture containing 30—80% of C2H4 in a non-reactive gaseous medium [C2H4 : steam = 0-3—4-0 (0-67—2-0)] through a solution containing 40—65% of (I) in an inert liquid, th e catalyst reaction zone being m aintained a t 195—300°/300—4000 lb./in.2 Similar claim is made for C3H 8 (C3H 8 : steam = 0-3—
2 0) a t 105—260°/>3000 lb./in.2 R. G.
D e h y d ra tio n of se c o n d a ry a n d t e r t i a r y alco h o ls a n d t h e ir c a rb o x y lic a c id e s te r s . N . Y. 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 T.
Ev a n s ( B . P . 485,485, 16.12.36. U.S., 23.12.35).—
Aq. mixtures containing one or more sec. or tert.
alcohols or their carboxylic esters are dehydrated by addition of a H 20-immiscible solvent comprising essentially a t least one aliphatic mixed or symmetrical ether of b.p. <50° and separating the H 20 either by direct azeotropic distillation Or by separation of an aq. layer followed by fractional distillation of the non-aq. layer. The dehydration of Pr^OH by means of EtOBuy or Me tert.-amyl ether, of BuyOH by EtOBuy, and of sec.-BuOH by Bu“.,0 is described.
R . G.
Cl. III.—ORGANIC INTERMEDIATES. 1015
P ro d u c tio n of ally l alco h o l. M. W. Ta m e l e
and H. P . A. Gr o l l, Assrs. to Sh e l l De v e l o p m e n t
Co. ( U . S . P . 2,072,016, 23.2.37. Appl., 21.4.36).—
CH2!CH‘CH2-OH is produced by hydrolysing CH2:CH-CH2C1 alone or in m ixtures the other con
stituents of which are more slowly affected, by heating a t 80—250° under increased pressure with an aq.
basic reagent. The use of Mg(OH)2, Ca(OH)2, and NaOH is claimed and batch and continuous processes
are described. A. H. C.
T r e a tm e n t of h a lo g e n a te d p o ly h y d ric alcoh ols.
H. P. A. Gr o l l and G . He a r n e, Assrs. to Sh e l l De v e l o p m e n t Co. (U.S.P. 2,070,990,16.2.37. Appl., 25.6.34).—Halogenated polyhydric alcohols having
>1 C l: 1 OH and a t least one lert. carbinol group are converted into epoxides or glycols by the action of bases (in H 20 ) ; further, hydroxyepoxides are hydrated by H 20 and a basic-acting substance. E.g.,
|i-methyl glycerol monochlorohydrin w ith aq. NaOH (1 equiv.) a t room temp, gives fi-methylglycide, b.p.
74—76°/26 mm. (70% of theory extracted by E t20), and a t 50° after 30 min. fi-methylglycerol, b.p. 115—
120°/ l -6 mm. (80% of theory); P-chloromethyl- glycide, b.p. 85°/l mm., p-ethylglycide, and diiso- butenyl dioxide, b.p. 170—180°/125 mm., are similarly
prepared. H. A. P.
M a n u fa c tu re of e th e r s . W. J . Te n n a n t. From
He n k e l & Co., G .m.b. H . ( B . P . 485,633, 23.11.36).—
Halohydrins of di- or poly-ethylene glycols are con
densed with phenols containing alkyl or cf/cZoalkyl radicals (< C4), preferably in alkaline media, tb yield ethers suitable for use as emulsifiers etc. The prep, of a m ixture of ethers from tetraethylene glycol monochlorohydrin and mixed phenols obtained by treating o-cresol w ith olefines (C8—C14) in presence of
HC104 is described. A. H . C.
M a n u fa c tu re of o rg a n ic p h o s p h a te s . S. L.
Ba s s, Assr. to D ow Chem. Co. (U.S.P. 2,071,323, 23.2.37. Appl., 19.1.35).—Triaryl phosphates useful as fungicidal and fireproofing agents and as plasticisers are prepared by the interaction of a P oxyhalide with p-C6H4Buv,OH (I) and, if required, other phenols, e.g., PhOH, C ftp y O H , cyclohcxy]phenol, or alkali salts thereof, a t <200° and preferably in presence of catalysts, e.g., Ca, Mg, Al, or chlorides of Mg, Al, or Fe. Examples a re : P0C13 (4), (I) (12 mols.), and MgCl2 (19 g.) a t 88—175° for 9 hr. give p-tert.- butylphenyl phosphate, m.p. 101°, and P0C13 (15 mols.), (I) (10 mols.), and MgCl2 (15 g.) a t 75—
120° for 2£ hr. give y-teit.-bulylphenylphosphoric acid dichloride, b.p. 150— 153°/6 mm., which by further treatm ent with mol. proportions of (I) and P-C10H 7O H gives di-p-tert.-butylpkenyl B- naphthyl phosphate. Similarly, Ph o-cyclohexyl- phenyl, b.p. 293—300°/6-4 mm., Ph di-, b.p.
2Sl°/5-5 mm., di-p-cMorophenyl, b.p. 287°/4 mm., di-o-tolyl, b.p. 284°/20 mm., di-o-anisyl-, b.p. 295°/4 mm., and dt-p -cy cl o/iexylphenyl, m.p. 81-5°, p-tert.- butylphenyl phosphate and Ph di--p-tert.-btdylphenyl phosphate, b.p. 261°/6 mm., are prepared. N. H. H.
M a n u fa c tu re of o rg a n ic e s te r s . E. I. D u
Po n t d e Ne m o u r s & Co. ( B . P . 4S6,560, 7.12.36.
U.S., 13.12.35).—Esters are prepared by interaction
of CO with an additive compound of a B halide (BF3) and an ether, preferably in presence of H 20 a t 150—
240°/400—900 atm ., liberating the ester from the resulting complex by adding more ether, distilling the ester, and again using the re-formed B F3-e th e r complex. The use of MeaO is claimed. A. H. C.
S e p a r a tio n of th e c o n s titu e n ts of o rg a n ic - in o rg a n ic a d d itio n c o m p o u n d s. E. I. D u Po n t d e Ne m o u r s & Co. (B.P. 486,563 and 486,886, 11.12.36. U.S., 13.12.35).—(a) Double compounds with B F3 are resolved into their constituents by adding a second org. compound which forms a complex with BF3 and distilling the m ixture, when the prim ary org.
compound is removed ; e.g., MeOAe is added to the complex B F3-Me20 and the Me20 removed by dis
tillation, or EtCO„H is added to B F3-AcOH and the AcOH removed by distillation, (b) The BF., complex is distilled a t such a pressure th a t the distillate differs in composition from the residue; tho distillation of BF3-AcOH complexes in several Stages a t 70°/15 mm.
and 150°/1 atm ., to distil off AcOH and B F3, respec
tiv e ^ , is described. S. C.
S e p a r a tio n of th e c o n s titu e n ts of o rg a n ic - in o rg a n ic a d d itio n c o m p o u n d s . E. I. D u Po n t d e N e m o u r s & Co. (B.P. 486,887, 11.12.36. U.S., 13.12.35).—Complexes of org. compounds with inorg.
halides (e.g., B F3) are treated with CaO or a halide of Na, Zn, A l , Cu, Pb, Fe, or Sn, the org. compound liberated by the formation of a new complex is separ
ated, and the B F3 recovered by heating. The treatm ent of B F3,2AcOH with N aF and NaCl is
described. A. H. C.
M a n u fa c tu re of o rg a n ic a c id s . E. I. D u Po n t d e Ne m o u r s & Co. ( B . P . 486,669, 8.12.36. U.S., 13.12.35).—In the production of org. acids or their derivatives by interaction of CO with a complex of a B halide (BF„) and an alcohol or a compound which may bo In'drolysed to such an alcohol, the org. acid is liberated from the B F3 complex by adding a Ca halide (CaF2) which itself combines with B F3. B F3 is recovered from the la s t complex by heating. The use of MeOH is specifically claimed. A. H. C.
O rg a n ic p ro c e s s e s em p lo y in g b o ro n -h a lo g e n - c o n ta in in g c o m p o u n d s. E. I. D u Po n t d e Ne m o u r s & Co. ( B . P . 486,877, 10.12.36. U.S., 13.12.35).—Hydrolytic decomp. of hydrated B halides, present in condensation and various other reactions in which th e B halide is used, during the separation of the org. reaction products is prevented by m aintaining the proportion of H 20 to B halide above the decomp. point of the association by continuous or interm ittent addition of H 20 ; in the case of H 20 and B F3 th e mol.
ratio is <2-3 : 1. Thus an org. acid, e.g., AcOH, may be recovered from a solution containing it and a hydrated B halide by steam-distillation, steam being added a t the same rate as H 20 distils off. R . G.
R eco v ery of lo w e r a lip h a tic a c id s . S o c . d e s Us i n e s Ch i m. Rh6n e- Po u l e n c ( B . P . 486,488, 2.7.37.
U . S . , 11.11.36).—Lower aliphatic acids are recovered from aq. solutions containing cellulose or its deriv
atives (e.g., AcOH obtained by pptg. cellulose acetate with H20 ) by hydrolysing th e cellulose to sugars sol.
in H 20 a t 160^—2 0 0 ° /> l atm . for 2— 15 min. in
1016 B R IT IS H CHEMICAL AND PHYSIOLOGICAL ABSTRACTS.—B.
absence of mineral acid and then recovering the org.
acid by azeotropic distillation or by extracting [e.g.,
with E t20 ). A. H . C.
P r o d u c tio n of w a s h in g , e m u ls ify in g , a n d d is p e r s in g a g e n ts . P . St e i n f e l d A.-G. (B.P.
486,S50 and Addn. B.P. 486,909, 5.11.36. Ger., 5.11.35).—(a) Capillary-active substances containing a t least one S 0 3H group are produced by interaction of a fatty , resin, or naphthenic acid (< C8) w ith an aliphatic oxidosulphonic acid (> C6). A product obtained from stearine and py-oxidopropanesulphonio acid is claimed, (b) Products as in (a) are obtained by introducing th e S 0 3H during tho reaction by heating glycidyl cetyl ether with R S 0 3M (M = alkali metal, R = H , ammo* or hydroxy-aryl). The use of p- 0 H ,CeH 4,S 0 3N a and p-N H 2,C6H .,S 0 3N a is claimed.
A. H. C.
P r o d u c tio n of h ig h e r a r o m a tic k e to -fa tty a c id s . H . A. Br u s o n, J . D. Ro b i n s o n, an d 0 . St e i n, Assrs. to Re s i n o u s Pr o d u c t s & Ch e m. Co. (U .S .P . 2,071,496, 23.2.37. Appl., 11.5.35).—Mono
basic keto-acids are prepared by the interaction of an arom atic hydrocarbon having an alkyl substituent of
> Cj with a saturated or unsaturated aliphatic dibasic acid anhydride of C2_ 8in presence of anhyd.
A1C13. E.g., succinic anhydride (100), sec.-amyl- benzcne (875), and A1C13 (295 pts.) a t 50° for 5-—6 hr.
give sec.-amylbenzoylpropionic acid. Similarly, sec.- amylbenzoyl-acrylic and -valeric acids are obtained.
N. H. H.
[M a n u fa c tu re of] x a n th ic fo r m a te s . J . H.
We r n t z, Assr. to E. I. D u Po n t d e Ne m o u r s & Co.
(U.S.P. 2,070,634,16.2.37. Appl., 5.7.35).—The prep, is claimed of esters and amides of the ty p e s : RO-CS-S-COJI (I), RO-CS-S-COJR' (II),
RO-CS-S-CO:S-CS-OR', and RO-CS-S-CO-NR"R"', in which R and/or R ' is an alkyl radical of < C8. E.g., K dodecyl xan th ate (III) and C0C12 in PhMe a t 40°
gives, on pouring into H 20 , the oily, H 20-insol. acid [ ( I ) ; R = C12H 25] ; the solution contains the cor
responding chloride, which with N H B u2 gives the dibutylamide, w ithN H 2Ph the anilide, and with C5H 5N a pyridinium chloride. Interaction of (III) with ClC02-C12H 25-w gives the ester [ ( I I ) ; R = R ' = C12H 25]
(not isolated). The products are insecticides, flotation agents, and vulcanisation accelerators.
H . A. P.
M a n u fa c tu re of cyclic a c e ta ls of fo rm a ld e h y d e . W. W . G ro v e s . From I. G. Fa r b e n i n d. A.-G. (B.P.
486,015, 27.11.36).—Cyclic acetals of CH20 are obtained in good yield by interaction of aq. CH20 with org. oxides, e.g., (CH2)20 , in presence of an acid catalyst, preferably in two stages, firstly a t about 50—100° in presence of H2S 0 4, H2C20 4, an org.
sulphonic acid, or an acid sulphate, and secondly in presence of HCI or H B r or a salt thereof having an acid reaction. The products m ay be distilled by running them into the corresponding glycol acidified with HCI and heated a t about 100— 130°. R. G.
M a n u fa c tu re of a m in o k e to n e s . 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. 485,377, 18.11.36).—V in y l o r p -h a lo g e n o e th y l k e to n e s a r e s t i r r e d a t 40—100°, if n e c e s s a r y i n a s o l v e n t a n d / o r u n d e r p r e s s u r e , w ith a li p h a t i c p r i m a r y o r sec. a m in e s
of < C6; prim ary amines react with one or two mols. of ketone according to the proportions present. E.g., CH„:CH-COMe (I) (75) is slowly added a t 50° to a m ixture of 4so-C7H 15*NH2 (115) and E tO H (150), the m ixture is stirred for 0-5 hr., E tO H is distilled off, and the residue distilled; a m ixture of mono- and di-y- kelobutylisoheptylamine, b.p. 130—131°/13 mm., is o btain ed; the corresponding product from iso- C6H 13-NH, has b.p. 127— 130713 mm. The in ter
action of (I) with C12H 25‘N H 2 is also described.
R . G.
S e p a r a tio n of lo w e r a lk y la m in e s . L. N.
Re d d i e. From Gir d l k r Co r p. (B.P. 486,821—2, 17.6.37).—The fact th a t, e.g., NHMc2 has a higher dissociation const, th an N H 2Me, NMe3, or N H 3 is utilised to separate it from mixtures of these com
pounds by (a) treating solutions of the hydrohalides with a q u antity of alkali (NaOH) equiv. to the am ount of alkylamines havhig dissociation consts. < 6 0 % of th a t of the sec. amine, or (b) treating a solution of th e amines with an am ount of mineral acid equiv. to th e sec. amine and removing the uncombined prim ary and tert. bases, e.g., by distillation. S . C.
M a n u fa c tu re of tr i- (4 - b u ta d ie n y l-l : 2 )-a m in e . I . G. F a r b e n i n d . A.-G. (B.P. 4 8 7 , 3 3 7 , 1 8 . 1 2 . 3 6 . Ger.,
2 0 .1 2 .3 5 ) .—Tri-(&Py-butadienyl)arnine (I), b.p. 84—
8 6 °/ 4 mm., 9 5 — 9 8 °/ 7 mm. (picrate, m.p. 7 8 ° ), is obtained by the action of N H 3 on CH2X -CH!C;CH2 (X = Cl, Br, I ) w ithout pressure a t about — 5 0 ° or under pressure a t 0—4 0 ° R . G.
R a c e m is a tio n of a m in o -a c id s . R . S. Bl e y
(U.S.P. 2,071,327, 23.2.37. Appl., 15.8.35).—
Optically active N H 2-acids are raeemised by tre a t
m ent with AcCl + AcOH (preferably a t 100°), followed if necessary by hydrolysis with HCI.
l-AcetyUyrosine hydrochloride, m.p. 244°, is described
as an interm ediate product. S. C.
S e p a r a tio n of a m in o -a c id s re a d ily so lu b le in w a te r a n d a m m o n iu m s u lp h a te . W. Gl u u d
and W. Ex e m p t, Assrs. to Be r g w e r k s v e r b a n d z u r
Ve r w e r t u n g v o n Sc h u t z r e c h t e n d e r Ko h l e n-
t e c h n ik G.m.b.H. ( U .S .P . 2,071, 2 S 2 ,16.2.37. Appl., 4.3.35. Ger., 18.5.34).—N H 2-acids and (NH4)2S 0 4 in solutions obtained by hydrolysing aminonitriles w ith H 2S 0 4 are separated by alternately adding N H 3 to ppt. ~(NH4)2S 0 4, removing excess of N H 3, and pptg.
N H 2-acid by adding more of the m ixture in solution and adjusthig the vol. The separation of (NH4)2S 0 4 and glycine or alanine is described. A. H. C.
P ro d u c tio n of a c id a m id e s . W . J . H u n d and L . Ro s e n s t e in, Assrs. to Sh e l l De v e l o p
m e n t Co. (U.S.P. 2,070,991, 16.2.37. Appl., 14.5.34).
—Acids or their derivatives (e.g., halides, anydrides, esters) are converted into amides by liquid N H 3. The use of esters and glycerides (e.g., sardine oil) and the recovery of anhyd. alcohols (glycerol) by distiUation are claimed and th e prep, of N H aAc from BuOAc or Ac20 , PrCO-NH2 from PrCOCl, and stearam ide, and mixed amides from coconut oil is described.
A. H. C.
M a n u fa c tu re of iso c y a n a te s [c a rb im id e s ]. H .A . Pig g o t t, F . S. St a t iia m, and Im p e r i a l Ch e m. In d u s t r i e s, Lt d. (B.P. 485,761, 24.11.36).—N
-Cl. I I I . —ORGANIC INTERM ED IATES. 1017 Substituted alkyl carbamates, NHR-CO,Alkyl, where
R = alkyl, cycloaXkyl, aralkyl, or aryl, are treated with COCl2, if deshed in presence of an inert solvent or diluent, e.g., C6H 6, and if necessary under pressure.
Examples describe the prep, of heptadecyl-, phenyl-, benzyl-, methyl-, o- and p-tolyl-, and cijdohexyl- carbimide and the mixed carbimides from the interaction product of coconut oil fa tty acid amides
with NaOMe. R. G.
H y d ro g e n a tio n of o rg a n ic m a te r ia ls [benzene].
Win g f o o t Co r p. (B.P. 487,285, 29.6.37. U.S., 21.11.36).—C6H g for hydrogenation is freed from catalyst poisons by treating with H 2S 0 4 to remove thiophen, and the C6H # fractionally distilled until the distillate is free from C S ,; it can be then readily hydrogenated to completion and the Ni catalyst re-used with practically no diminution in activity.
R . G.
P ro d u c tio n of a lk y l-s u b s titu te d a r y l h y d ro c a rb o n s . C. A. Th o m a s, Assr. to Sh a r p l e s So l
v e n t s Co r p. (U.S.P. 2,072,061, 23.2.37. Appl., 28.8.33).—Paraffins (C 8_ 30) are partly (< 5 0 % ) mono- chlorinated, so avoiding poly chlorination, the resulting m ixture is condensed without separation with an aryl compound in presence of a catalyst (AlCla), and the unchlorinated hydrocarbon and alkyl substitution product are recovered. The chlorination of C12H 26 and production of C10H 25Ph are described.
A. H. C.
(A—C) M a n u fa c tu re of a r y l s u b s titu te d m o n o - olefines a n d (B) d e riv a tiv e s th e re o f. Distillers
Co., Ltd., H. M. Stanley, G. Mink o ff, and J . E.
Youell (B.P. 486,520, 486,573, and 486,574, [a—c]
30.10.36, [b] 12.2.37).— (a) Aromatic hydrocarbons (I) (C8H„) are condensed with mono-olefines (II) of C3_ 5 (CHoICHMe) by means of conc. H 2S 0 4 a t >25°
(0—10°), the spent acid is removed, and the product washed preferably by countercurrent with a relatively small quantity of H 2S 0 4 which is afterwards used for further condensations. A m onoalkylated product predominates when the ratio of (I) to (II) is < 2, whilst with 1 : 1 mols. a large am ount of dialkylated product (III) is obtained. (II) m ay be an unpurified m ixture of olefines such as is obtained in the cracking of oils and may contain C2H 4, which is practically unchanged in th e reaction, (b) The monoalkylated products of (a), particularly P h lV 3. are subjected to pyrolysis a t 600—800° (650—750°), the reaction being directed to the production of styrene hydrocarbons together with CH4; therm al dehydrogenation is suppressed by addition of the products of such a reaction, viz., H 2 or, e.g., CPhMe!CH2, if deshed with a diluent (steam), the linear gas velocity being several times the crit. velocity so as t o ensure turbulence. A crude pyrolysis product consisting of approx. 25% of CHPh:CH2, 25% of CPhMe:CH2, and 50% of un
changed P h P r0 m ay be subjected to co-polymerisation, e.g., in absence of 0 2 and catalysts a t 125° for a week, the resulting resin separated, and unconverted reactants returned with more PhPr^ to the pyrolysis stage, (c) The dialkylated products (III) of (a), which may be mixed with monoalkylated products, are subjected to pyrolysis as in (b) a t such a high linear gas velocity th a t < 70% of (III) undergoes reaction in a
3 z (B.)
single passage through the pyrolysis tube to give divinylated aromatic hydrocarbons. E.g., p- C6H4Pr°2 gives ?)-C6H4(CMe:CH0)„ and p - C J L P A gives ?j-CgH 4(CH:CH,)2 + CH4. ' R. G.
M a n u fa c tu re of d e riv a tiv e s of p y re n e . G. W.
Jo h n s o n. From I. G. Fa r b e n in d. A.-G. (B.P.
485,874, 30.11.36).—Pyrene derivatives which give yellow solutions showing green fluorescence in org.
solvents are obtained by heating pyrene with an aliphatic compound containing > C4 and < 2 halogen (Cl) atoms, e.g., CHC13, in presence of anhyd. A1C13 until evolution of HCI ceases, if desired in presence of a non-reacting solvent of higher b.p., e.g., PhCl.
R . G.
M a n u fa c tu re of su lp h o n ic a c id s of th e n a p h th a le n e s e rie s . J . R . Ge ig y A.-G. (B.P. 485,971, 10.9.37. Switz., 11.9.36).—N H 2 in l-amino'-p- naphtholsulphonic acids (I) is replaced by S 0 3H by heating an aq. solution or suspension of the diazo- compound of (I) with Na2S 0 3, preferably in presence of a metal (Cu, Zn, or Al) and/or salt thereof; the S 0 3H so introduced m ay be replaced by H by heating with H 20 or acids. The prep, of the alkali salts of (3- naphthol-l : 4-disulphonic acid and its 6-ArO,- and 6-/?r-derivatives, and Q-broino-p-naphtholA-suIphonic
acid is described. R . G.
M a n u fa c tu re of c o n d e n s a tio n p ro d u c ts . G. W.
Jo h n s o n. From I. G. Fa r b e n i n d. A.-G. (B.P.
485,883, 7.1.37).—Hydrophobic condensation products which are valuable interm ediates for the prep, of dyes, textile assistants, etc. are prepared by heating in the liquid phase approx. equimol. proportions of aromatic compounds containing OH, N H 2, or !NH and in addition a t least one further such group or a C 02H or an enolisable side-chain, and additive compounds (cf.
B.P. 355,281; B., 1932, 72) formed by addition of aliphatic ap-unsaturated ap-dicarboxylie acids or their derivatives to natural or synthetic resins and oils of unsaturated character. E.g., the additive compound from colophony or abietic acid with maleic anhydride is heated with ;p-C6H 4(NH2)2 in xylene a t 100° fo r 1 h r . ; the ppt. has acid val. 116 and can be diazotised.
R. G.
P r e p a r a tio n of A '-a lk o x y alk y lary lsu lp h o n - a m id e s . B . C. Br e n, Assr. to E. I. D u Po n t d e
Ne m o u r s & Co. (U.S.P. 2,071,917, 23.2.37. Appl., 12.6.35. Can., 18.2.35).—iY-Alkoxy alky larylsul phon- amides of high b.p. are prepared by the interaction of an arylsulphonamide with an alkoxyalkyl halide in aq. NaOH. E.g., j)-CfiH 4Me*SO,-NH2 (171), H ,0 (200), NaOH (40), and 0Me-[CH2]3"Cl (120 pts.) boiled for 30 hr. give p-toluenesulphon-y-methoxyprapylamide.
Similarly, ■p-toluenesulphondimethoxyethylamide an d bis-'p-toluenesulphonaniidodiethyl ether are prepared.
The products are compatible with resins, rubber, etc.
N. H . H.
P ro d u c tio n of o rg a n ic p h o s p h o ru s c o m p o u n d s.
Ce l l u l o id Co r p. (B.P. 486,760, 3.11.36. U.S., 20.11.35).—The interaction in a single stage of PCb, H 20 , and a homocyclic nuclear OH-compound (cresol) is claimed. Apparatus and procedure for the prep, of P 0 (0 -C 6H 4Me)3, and its purification by Na2S, followed by nascent H, are described. "H. A. P.
1018 B R IT IS H CHEMICAL AND PHYSIOLOGICAL ABSTRACTS.—B.
[M a n u factu re of] a r y lp h o s p h o ric a c id h a lid e s [p la s tic is e rs ], S. L. Ba s s, Assr. to Dow Chem.
Co. (U.S.P. 2,071,017, 16.2.37. Appl., 13.7.36).—The prep, by standard methods of mono- and di-aryl-
Co. (U.S.P. 2,071,017, 16.2.37. Appl., 13.7.36).—The prep, by standard methods of mono- and di-aryl-