Geochem istry.
In ter-relation b etw een d ia to m s, th eir ch em ical environm ent, and u p w ellin g w a te r in th e sea, off the co a st of S ou th ern C alifornia. E. G. Mo b e r g
(Proc. N at. Acad. Sci., 1928, 14, 511—518).
D isso lv ed and su sp en d ed m in era l m a tter in Colorado R iver. W. D. Collins and C. S. H o w a r d
(Ind. Eng. Chein., 1928, 20, 746—748).—In 1925—
1927 th e dissolved solids varied from 250 to 1500 in lO*', th e to ta l hardness calculated as calcium carbonate ranged from 130 to 640 in 10°, and the non-carbonate hardness from 38 to 400 in 106.
R . A. Pr a t t.
Rare g a s e s fr o m th er m a l sp r in g s and the earthquakes of A p ril 1 4 and 18, 1928, in B u l
garia. N. P . Pe n t c h e v (Compt. rend., 1928, 187, 243—244).—The composition of rare gases evolved from therm al springs hi B ulgaria has been found to be unchanged by earthquakes. No certain conclusion can be reached concerning the constancy or otherwise of their radioactive properties. C . W. Gi b b y.
P robable id e n tity of g a g e ite w ith tephroite.
S. G . Go r d o n (Proc. Acad. N at. Sci. Philadelphia, 1928, 79 (for 1927), 207—208).—A tabu lation of the chemical composition, optical d ata, crystal angles, etc.
of gageite from F rank lin Furnace, New Jersey (A., 1910, ii, 96S), suggests th a t this m ineral is th e same as
tephroite. L. J . Sp e n c e r.
A rfvedsonite, rieb eck ite, and cro cid olite from Greenland. S. G . Go r d o n (Proc. Acad. N at. Sci.
Philadelphia, 1928, 79 (for 1927), 193—205).—
Descriptions w ith optical d a ta are given for these amphiboles from the nepheUne,-syenites of south Greenland. The following analyses are given of arfvedsonite from different localities. I by H. S . Wa s h i n g t o n, I I b y E . V. Sh a n n o n, and I I I by F.
Wy n k o o p. They are interpreted as m ixtures of the arfvedsonite molecule (R20 ,3 R 0 ,4 S i0 2) and riebeckite molecule (R20 ,R 20 3,4Si02), usually w ith an excess of H20 3, where R 20" is largely N a20 , and RO and R 20 3 are chiefly FeO and F e20 3.
S i0 2. T i0 2. a i2o3. Fo20 3.. FeO. MnO. MgO.
I. 43-52 1-73 5-30 11-12 22-39 1-13 1-09
II. 4 3 0 8 0-83 4-44 8-06 28-97 0-70 0-32
in . 49-11 0-78 1-1G 9-23 25-50 1-13 0-18
CaO. N a20 . K 20 . F. H 20 . Total. d.
i. 2-21 7-39 1-83 0-88 1-20 100-26 3-465
n. 4-08 6-88 3-28 _ 1-10 100-74 3-447
m . 0-77 8-01 2-89 0-29 1-12 100-05 4-410
Totals less O for F t. I, also Z r02 O'84. II, also BaO trace.
Riebeckite occurs in parallel growth on iegirine
crystals, and crocidolite in parallel growth on arfvedsonite. L . J . Sp e n c e r.
O livine of L inosa (P elagic Isla n d s). G.
Ca r o b b i (Atti R. Accad. Lincei, 1928, [vi], 7, 654—
660).— Crystallographic and analytical d ata are given for two specimens of transparen t olivine, one greenish- yellow (d 3-410), th e other reddish-yellow (3 3-462).
These contained respectively: FeO, 12-43 and 11-06% ; NiO, 0-12 and 0-18% ; CoO, 0-13 and 0-10% ; and, more notew orthy, PbO, 0-20 and 0-26%. I t is sug
gested th a t the lead occurs as th e result of an iso
morphic substitution of magnesium. The two com
pounds (Fe,Co,Ni,Mn)2S i04 and (Mg,Ca,Pb)2S i0 4 constitute 77-5% an d 22-5%, respectively, of the specimens analysed. F . G . Tr y h o r n.
In tru siv e rock of M uno (L uxem burg) and m e ta m o rp h ism p rod uced b y it. A. L . Ha c- q t j a e r t (Natuurwetensch. Tijds., 1928, 10, 73—88).—;
The intrusive veins consist chiefly of felspar an d biotite, w ith inclusions of calcite, quartz, apatite, zircon, chlorite, an d pyrites, and the m aterial is classed as a kersantite. The inclusions of calcite are of magm atic origin. I t is deduced th a t th e intrusions occurred a t relatively low tem peratures, and th a t the whole was subsequently subjected to hydrotherm al action. The action of the solutions, which were rich in magnesium salts, has resulted in considerable im pregnation of the surrounding rock with biotite.
S. I. Le v y.
S eries of la v a s of S outhern S erb ia . J . To m i t c h
(Compt. rend., 1928, 187, 133—136).—Analyses of five specimens are recorded. C. W . Gi b b y.
A lk a li-la v a s fr o m M ount N im ru d , A rm en ia.
G . T. Pr i o r (Min. Mag., 1928, 21, 485—488).—
Micro-sections of rocks from M ount N im rud showed th e presence of anorthoelase, sogirine, and soda- amphiboles. Complete chemical analyses were there
fore m ade of three of the rocks (soda-rhyolite, pan- telleritic trachyte, and trachyandesite), showing about 6% N a20 , an d a relation to the soda-rocks of the R ift Valley in E ast Africa is suggested.
L , J . Sp e n c e r.
J u lien ite. A. Sc h o e p (Natuurwetensch. Tijds., 10, 58—59).—Blue microscopic needles, forming a th in layer on a white talcose schist a t Chamibumba, near K atang a, having refractive indices of 1-645 parallel to and 1-556 perpendicular to the elongation, respectively, an d readily soluble in cold w ater, appear to consist of a h yd rated cobalt chloronitrate.
S. I. Le v y.
Organic Chemistry.
S teric h in d ran ce. W . Hu c k e l (Ber., 1928, 61, active condition), is usually calculated from th e [B], 1517— 1524).—An a tte m p t is m ade to differentiate tem perature coefficient of th e velocity coefficient k.
between th e spatial an d chemical factors generally The “ action co nstant ” a, which expresses the confusedly involved under th e term “ steric hindr- probability of encounter of th e active surfaces of the ance.” The modified T rau tz formula k —ae-"8^ is molecules and, in addition to th e activation energy, used in which q, th e activation energy (mean energy controls th e velocity coefficient, is obtained by required to bring th e reacting molecule into the sub stituting the calculated value of q in the value
988 B R IT ISH CHEMICAL ABSTRACTS.----A.
■of k determ ined a t any definite tem perature. E x am ination of th e d a ta recorded by Vavon for the hydrolysis of th e cis- and iraws-o-isopropylcf/cZohexyl hydrogen succinates, cis- and irans-o-w-propylcycZo- hexyl hydrogen phthalates, and bornyl and isobornyl hydrogen ph th alates shows th a t considerable differ
ences in th e rates of reaction m ay depend on great
■differences between q or a b u t a uniform in terp re
ta tio n of steric hindrance cannot be deduced from th e results. E xam ination of th e rates of hydrolysis
•of n-propyl, n- and iso-butyl, isoamyl, /sopropyl,
■sec.- and tert.-butyl acetates show's th a t the activation
•energy and action constants are approxim ately th e .same for esters of prim ary alcohols. The activation
•energy of esters of te rtia ry alcohols is m uch greater
•and th e action constants are much smaller th a n those
■of esters of prim ary alcohols, both influences dim inish
ing th e ra te of hydrolysis. H . Wr e n.
T h e r m a l d isso c ia tio n of ethan e, p rop an e, n- an d iso -b u ta n e. R . N. Pe a s e (J. Amer. Chem.
.Soc., 1928, 50, 1779— 1785).—The gases are passed thro u g h P yrex glass tubes a t 625° and 650° under 1 atm . pressure. T he to ta l ra te of dissociation increases w ith th e com plexity of th e molecule. The two m ain reactions arc dehydrogenation and de- m ethanation. The ratios of hydrogen to m ethane
•decrease in th e sequence, ethane, propane, w-but- -ane. i'soButane decomposes a t ab o u t th e same ra te as n-butane b u t gives relatively m uch more hydrogen. »-B u tane does n o t undergo appreciable secondary reaction. R eactions appear to be som e
w hat m ore rap id th a n norm al in th e first few seconds, b u t dilution experim ents indicate a change of th e first order. The tem perature coefficients are, as a m inim um , 1-5—2 per 25°, giving a m inim um ac tiv ation energy of 25,000—50,000 g.-cal. H . Wr e n.
C ontrol of th e m o l. w t. of liq u id h y d roca rb on s p rod u ced b y e le c tr ic a l d isc h a r g e in ethan e.
S . C. Li n d and G. Gl o c k l e r ( J . Amer. Chem. Soc., 1928, 50, 1767— 1772).—Silent, corona, and high- frequency discharges all cause th e condensation of -ethane to liquid products w ith liberation of perm anent gases. The average mol. w t. of th e liquid products has been regulated between 467 and 105 by controlling the tim e th a t th e first products, either gaseous or liquid, are allowed to rem ain in th e discharge tube.
Prolongation of th e action causes increase in mol. w t.
of th e products. H. Wr e n.
W urtz reaction . F a cto rs in v o lv ed in th e p r e p a ra tio n of octane. H . F . Le w i s, R . He n d r i c k s, and G. R . Yo h e (J. Amer. Chem. Soc., 1928, 50, 1993— 1998).—A m ethod has been developed for preparing octane, b. p. 124-2— 124-8°, rff 0-7044, rajj 1-3961, from n-h u ty l bromide an d sodium in 65—70%
yield based on th e b utyl bromide. O ptim al condi
tions consist in th e use of an excess of sodium which need n o t exceed 50% , a volum e of ether two and a half tim es th a t of th e b u ty l bromide, low tem perature, a period appropriate to each set of conditions, an d fine sodium wire. A gitation is of m aterial advantage.
Traces of w ater are unexpectedly detrim ental, b u t sufficient dehydration is secured if th e ether is dried -over calcium chloride an d distilled over sodium.
The presence of acetonitrile does n o t favour th e form
atio n of octane. B utene and a t least tw o higher satu ra te d hydrocarbons, possibly dodecane and hexa- decane, are also produced. H . Wr e n.
H exa-fei-t.-b u ty leth in y le th a n e. P. L . Sa l z b e k g
an d C. S. Ma r v e l (J. Amer. Chem. Soc., 1928, 50, 1737— 1744).—The hydrocarbon is undissociated at the ordinary tem perature and undergoes rearrange
m ent when the tem p erature is raised. Cleavage by alkali m etals indicates th a t th e stab ility of th e central ethane linking is interm ediate between th a t of the corresponding linking in dibenzyl and hexaphenyl- ethane.
/eri.-B utylacetylene is converted by the successive action of m agnesium eth yl brom ide an d ethyl chloro- form ate into tri-teit.-butylethinylcarbinol,
(CMe3-C:C)3C-OH, m. p. 100— 102-2° (corr.) (additive compound w ith stannic chloride), which is isomerised by concentrated sulphuric acid to th e ketone
(CMe3-C:C)2-C:CH-CO-CMe3, m. p. 109-5—110-5°
(corr.). The carbinol in light petroleum is trans
formed by phosphorus tribrom ide in to the corre
sponding bromide, ap p a re n tly existing in twro forms, m. p. 69—70° (corr.) and 177— 178° (corr.), respect
ively. Tri-tert.-butylethinylmethyl acetate, in. p.
144-5— 145-5° (corr.), from th e carbinol, potassium, and acetic anhydride or from th e brom ide and silver acetate, is hydrolysed by potassium ethoxide to the original carbinol. W ith molecular silver in the presence of eth er th e bromide affords hexa-tnrt.-butyl- ethinylethane, (CMe3-C:C)3C-C(C:C-CMe3)3, m. p. 130—
131° (corr.), rearranged in xylene a t 140° to a hydro
carbon, C38H 54, m. p. 174—175° (corr.). Tri-tert.- butylethinylacetic acid, (CMe3’C:C)3C-C02H, m. p.
202—205°, is p repared from th e ethane by the successive action of sodium -potassium alloy and carbon dioxide or from th e brom ide by treatment w ith m agnesium and carbon dioxide. H. Wr e n.
A ctio n of n a sc e n t th iocy a n o g en on isoprene and d im eth y lb u ta d ien e. H . A. Br u s o n and
W . A. Ca l v e r t (J. Amer. Chem. Soc., 1928, 50, 1735— 1737).—An additive compound, C7H 8N 2S2, m. p.
76-—77° (corr.), is form ed b y th e addition of bromine to isoprene an d sodium thiocyanatc in glacial acetic acid a t 5— 6°. A sim ilar substance, C8H 10N2S2, m. p.
130° (corr.), is produced from ¡3y-dimethylbutadiene.
The com pounds are useful for the identification of
th e hydrocarbons. H. Wr e n.
R e a rra n g em e n ts of th e trip le lin k in g. H. H.
Gu e s t (J. Amer. Chem. Soc., 1928, 50, 1744— 174G).
—A°-Heptinene is prepared in 74% yield by the ad dition of dibrom oheptane to finely-divided potass
ium hydroxide covered w ith m ineral oil a t 250 . I t is converted into an isomeric hydrocarbon by passage over soda-lim e a t 380° or over pumice at 350°. The reverse transform ation is apparently effected by sodam ide suspended in m ineral oil at
160°. H. Wr e n.
M o d ifica tion of th e A d a m s' m eth od of pre
p a r in g a lk y l io d id es. H . S. Ki n g (Proc. Nova Scotian In s t. Sci., 1927, 16, 87—91).—A m odified form of ap p aratu s is described which can be con
stru cted from commonly available p arts. H. Wr e n.
ORGANIC CHEMISTRY. 989 C olorim etric d eterm in a tio n of eth ylen e ch loro-
hydrin. M. B. Sa p a d i n s k i (Z. anal. Chem., 1928, 74, 273—275, and J . R uss. Phys. Chem. Soc., 1928, 60, 695—697).—The solution containing ethylene chlorohydrin is m ixed w ith diazobenzenesulphonic acid and warm ed to 25°, w hereby complete oxidation of the -CH2-OH group to > C !0 occurs. The alkali hydroxide, which induces condensation, is no t added until the first change is com plete; subsequently the mixture is heated a t 50°. F or m easurem ent, a solu
tion o f “ B ordeaux-Lafitte ” in benzene, standardised by use of known am ounts of ethylene chlorohydrin,
is employed. H. Wr e n.
D eriva tives of «-h ep tan e. R . T. Di l l o n and H. J . Lu c a s (J. Amer. Chem. Soc., 1928, 50, 1171—
1714).—Heptan-8-ol, m. p. —37-2° to —41-5°, b. p.
153-4— 154-4° (corr.)/745 m m ., d f 0-8175, rif 1-4173, is prepared from magnesium «-propyl bromide and ethyl form ate. Heptan-y-ol, from magnesium w-butyl bromide an d propaldehyde, has b. p. 152-7— 154°
(corr.)/745 m m ., rif 1-4201. H. Wr e n.
C on stitu tion of p h ytol. F . G. Fi s c h e r [with K. Lo w e n b e r g] (Annalen, 1928, 464, 69—90).—The ketone obtained by W illstatter and co-workers (A., 1911, i, 144; 1919, i, 448) by the oxidation of phytol, and regarded b y them as having the form ula C ^H ^O , is now shown to be C18H 360 , since glycollaldehyde is formed when phytol ozonide, a C20 compound, is reduced either by m eans of zinc and acetic acid or by means of hydrogen and palladised calcium carbon
ate. If phytol is regarded as being built up of reduced isoprene units, it is m ost likely to be (cf. geraniol and farnesol) tetramethyl-AP-hexadecen-a-ol, CHMe2-[CH2]3
-CHMe-[CH2].J-CHMe-[CHVJ3-CMe:CH-CiLj’OH, which when ozonised etc. Would produce glycollalde
hyde and Cx^-trimethylpentadecan-fS-one. The latter substance has accordingly been synthesised : H ydro
genation of farnesol in m ethyl alcohol in presence of palladised calcium carbonate affords a 40% , whilst hydrogenation in S0% m ethyl alcohol in presence of palladous chloride gives no t less th an an 80% yield of farnesane [{J£k-trimethyldodecane], b. p. 119-5—
120711 mm ., d f 0-7682, n f 1-4303. Reduction of farnesyl acetate in ethyl acetate in presence of palladised calcium carbonate gives a little farnesane, but m ainly th e desired hexahydrofaniesol [yrfi-tri- methyldodecanol], b. p. 151— 152-5°/10 mm., d f 0-8491, n f 1-4487. The la tte r is converted by phos
phorus tribrom ide in light petroleum into y-i\\-tri- methyldodecyl bromide, b. p. 150— 154°/10 mm., which w ith eth y l sodioacetoacetate gives ethyl yr)Ari- rnethyldodecylacetoacetate, b. p. 192— 195°/10 mm.
The latter, w hen hydrolysed by cold and then by warm 3% methyl-alcoholic potassium hydroxide, affords sKVtrimethylpentadecan-[3-one, identical in properties .w ith th e ketone, ClgH 360 (b. p. 173-5—
l74o/10 mm. or 294—295°/708 mm., d f 0-8323, ftjE,’ 1-4432). T he two semicarbazones melted alone, or when mixed, a t 66—67°. The ketone and phytol therefore have th e constitutions m entioned above.
E. E . Tu r n e r.
S p a tia l con fig u ra tio n of tw o c is -f rans-ethylenic iso m er id es [¡3e - d im e th y l - Av - h e x e n e -£ s-d io ls].
Bo u r g u e l and R a m b a u d (Compt. rend., 1928, 1 8 7 , 383—384).—The ¿ra«s(a)-form, 111. p. 76—77°, of (k-dimethyl-Av-hexene-|3s-diol (Zalkind, A., 1923, i, 176) is shown to be a solid solution of 5 p a rts of th e cis(p)-form, m . p. 69—70°, an d 1 p a rt of the tru e tTnns(y)-modification, m. p. 101°, obtained also by reducing fls-dimethyl-A^-hexinene-pE-diol w ith sodium and alcohol. W hilst dehydration of the « ¿¡-modific
ation gives a y-oxide (Zalkind, loc. cit.), th e trans- com pound affords a m ixture of (is-dimethyl-Av*- hexadien-^-ol and fic-dimethyl-A'^'-hexatriene.
H . Bu r t o n.
C on d en sations of g ly cero l. Ra n g i e r (Compt.
rend., 1928, 1 8 7 , 345—346).—The action of fused sodium acetate on heated 95% glycerol followed by tre a tm e n t of the product w ith acetic anhydride affords th e following compounds : diglyceryl tetra
acetate, (C3H 5)20 (0 A c)4, b. p. 164— 165°/2 m m .;
triglyceryl penla-acetate, (C3H 3)30 2(0A c)5, b. p. 194—
195°/2 m m .; tetraglyceryl hexa-acetate, b. p. 224—
225°/2 m m .; pentaglyceryl hepta-acetate, b. p. 254—
255°/2 m m .; hexaglyceryl octa-acetate, b. p. 284—
285°/2 m m .; heptaglyceryl ■nona-acetate. H . Wr e n.
A cetylen ic g ly cer o ls co n ta in in g a s tr a ig h t chain of five carhon a to m s. R . Le s p i e a u (Bull.
Soc. chem., 1928, [iv], 4 3 , 607— 662).—Ss-Dichloro- Aa-pentinen-y-ol, b. p. 90—91°/12 m m ., d'a 1-306, nD 1-500, is obtained from dimagnesium acetylenyl bromide and acraldehyde dichloride. I t is converted by 10% potassium hydroxide into z-chloro-y8-oxido- bf-pentinene, b. p. 58—60°/20 mm., da 1-159, n[t 1-472, which is h ydrated to z-chloro-&.a-pentinene-y8- diol, b. p. 131— 132°/16 m m ., dla 1-289, n g 1-501. The la tte r substance w ith sodium m ethoxide affords s-niethoxy-Aa-pcnlinene-y$-diol, b. p. 100°/3 mm., dP 1-12, n f 1-473, whereas it is hydrolysed by w ater in presence of calcium carbonate to A“-pentinene-ySc-lriol, b. p. 156— 15974 mm., d% 1-217, n f 1-489 (triphenyl- urethane, 111. p. 204—206°). All the acetylenic com
pounds re act w ith alcoholic silver n itrate, whereas only th e dichlorohydrin and epichlorohydrin yield precipitates w ith am m oniaeal cuprous chloride. The isolation of two a^vfi-ietrdchhro-M-octinev^y^-diols, 111. p. 139— 139-5° and 96-5—97-5°, respectively, is described.
z-Methoxy-a.^-oxido-Ay-pentinene, b. p. 75—76°/
15 m m ., cP 4-024, 1-4573, is prepared from chloro-acetaldehyde and the com pound
OMe-CH2-C:C-MgBr. I t is converted by hydrogen chloride into v.-chloro-z-metlioxy-Ay-pcntinene-$-ol, b. p.
117-5— 118-5°/12 mm., d2i 1-172, n f 1-485, and by w ater into s-met?wxy-£sr-pentinene-ci^-diol, b. p. 155—
156°/12 m m ., ds 1-1274, < - 1 - 4 8 1 ; with boiling m ethyl alcohol containing a little sulphuric acid it affords o.z-dimethoxy-&?-penti'h£ne-$-ol, b. p. 207—
210°/10 m m ., da 1-0508, rif 1-4608. yS-Dibromo-z- methoxy-Av-pentinene-x$-diol has m. p. 51—52°, b. p.
I9 2 7I I mm. H. Wr e n.
U se of m a g n e s iu m a lk o xid es in th e p rep a r
ation of eth ers. V. Ce r c h e z (Bull. Soc. chim., 1928, [iv], 43, 762—768).—W hen treated on a brine- b ath w ith 2 mols. of m ethyl sulphate, magnesium alkoxides afford m ethyl ethers in /0 80% yield.
W ith eth yl sulphate at 120— 130° th e corresponding
990 B R IT ISH CHEMICAL ABSTRACTS.— A.
eth y l ethers are obtained in 60% yield. The follow
ing ethers have been prepared by this m e th o d : m ethyl «-butyl ether, b. p. 70°; m ethyl isoamyl ether, b. p. 90—91°; m ethyl cycZohexyl ether, b. p.
133— 135°; methyl sco.-octyl ether, b. p. 158° (yield 15%), octene, b. p. 125°, being also produced; eth yl w-propyl ether, b. p. 63-6°; ethyl «-butyl ether, b. p.
91°. Magnesium benzyloxide and m ethyl sulphate give no definite product. The alkoxides are readily obtained b y trea tin g magnesium am algam, prepared in th e dry way, w ith th e alcohol; th e action proceeding very readily w ith propyl an d benzyl alcohols and cycZohexanol, less readily w ith butyl, isoamyl, and octyl alcohols. W hen eyc/oliexanol is heated a t 120°
w ith 2 mols. of m ethyl alcohol and 1 mol. of sulphuric acid a considerable am ount of c?/c/ohexene is formed.
R . Br i g h t m a n.
H yd ro gen ation of eth ers. A. Ma r t y (Compt.
rend., 1928, 187, 47—49).—P ropyl, isopropyl, b utyl, am yl, and isoamyl ethers suffer fission when passed w ith hydrogen over reduced nickel a t 250—300°.
A t 180°, phenetole is sm oothly converted into cyclo- hexane an d ethyl alcohol, whereas a t 250° this reaction is accom panied by th e production of eth ane and phenol. (3-Naphthyl m ethyl and ethyl ethers decom pose a t 2S0° in both directions; th e arom atic com ponents are fu rth e r hydrogenated to di- and tetira-hydronaphthalene and tetrahydro-p-naphthol.
Guaiacol a t 180° u n d e r 300 m m. gives th e m ixed ether OH-C6H 10-OMe, together w ith pyrocateehol and phenol (partly reduced to cyclohexanol). U nder sim ilar conditions, diphenyl ether affords dicf/dohexyl ether, phenol, cycZohcxanol, benzene, a n d c//cfohexane.
H . Wr e n.
A c tio n of d isilico n h ex a ch lo rid e on ether.
S. Ki p p i n g and R . A. Th o m p s o n (J.C.S., 1928, 1989— 1990).—Disilicon hexachloride, like silicon tetrachloride (K ipping and M urray, this vol., 79), reacts to a slight ex ten t w ith pure ether to yield a com pound from which alcohol is formed on hydrolysis w ith sodium hydroxide. I t is suggested th a t an additive com pound is first form ed which is p a rtly decomposed into eth y l chloride and chloroethoxy- silicon derivatives. J . W . Ba k e r.
P re p a r a tio n of n o r m a l su lp h u r ic e ste r s. R . Le v a il l a n t (Compt. rend., 1928, 1 8 7 , 234—236).—
Alkyl sulphates are prepared by th e action of alkyl n itrites on alkyl chlorosulphonates, C1-S02,0 R + 0 . N • 0 R '= OR• S 0 2• 0 R ' -¡-N0 Cl. Thus m ethyl chloro- sulphonate and m ethyl n itrite a t 80— 145° give m ethyl sulphate in 40% yield. E th y l sulphate, in 55% yield, is derived from ethyl n itrite arid ethyl chlorosulphon- a te a t SO— 100°. H . Wr e n.
O rgan ic tita n o u s com p o u n d an d th e p rep a r
a tio n of s o lu tio n s of tita n o u s sa lts. D . W . Ma c- Co r q u o d a l e a n d H . Ad k i n s (J. Amer. Chem. Soe., 1928, 5 0 , 193S— 1939).—T etraeth yl tita n a te is reduced b y sodium an d eth y l alcohol to im pure ethyl tita n ite , E t3T i0 3, which can be fu rth er purified by heating a t 156°/S— 10 m m ., w hereby some unchanged eth yl tita n a te distils. T he final product is a dark blue, am orphous solid containing ab o u t 87-4% of tita n ite . I t reduces arom atic nitro-eom pounds to amines very readily arid arom atic aldehydes to alcohols somewhat
m ore slowly. H. Wr e n.
P re p a ra tio n of e ste r s. M. K o t a k e and Y.
Fu j i t a (Bull. In st. Pliys. Chem. Res., Ja p a n , 1928, 7, 734—739).—N early q u an titativ e yields of various esters (including those of: stearic, succinic, benzoic, malonic, maleic, cinnamic, pyromucie, an d salicylic acids) are obtained by heating th e acid w ith a slight excess of alcohol, a q u a n tity of sulphuric acid equiv
alent to th e alcohol used, and anhydrous aluminium sulphate a t 100°. Only a 71% yield was obtained in th e case of oxalic acid. J . W . Ba k e r.
A ctio n of h y d rog en b ro m id e on organic e ste r s a t th e ord in ary p ressu re . M. S£on
(Com pt. rend., 1928, 187, 131— 133).—The action of hydrogen bromide under varied conditions of tem
p eratu re b u t a t atm ospheric pressure on am yl formate, am yl salicylate, benzyl acetate, benzyl benzoate, allyl acetate, eth y l acetoacetate, an d «/cZohexyl acetate leads to th e form ation of th e organic acid and the alkyl, benzyl, or c?/c/ohexyl brom ide. Phenyl acetate or benzoate is n o t decomposed under these conditions.
H. Wr e n.
C atalytic d eco m p o sitio n of o leic acid. B.-.M.
Ma r k s and H . C. Ho w a r d, ju n .—See this Vol., 968.
P r e se n c e of a n ew fa tty a cid in a fish oil.
H . Ma r c e l e t (Compt. rend., 1928,187, 145—146).—
In. addition to stearic, palm itic, and an unidentified acid, m. p. 46— 47°, dorosomic acid, C17H w0 2, ni. p.
55°, is isolated from Dorosoma vasus, Bloch; the methyl ester, m. p. 30°, an d th e barium salt are
described. H. Wr e n.
K eta zin es of lsevu lic acid an d Isevulhydrazide.
C. W . Be n n e t t (J. Amer. Chem. Soc., 1928, 50, 1747— 1748).—Sodium lsevulate and hydrazine hy d ra te in boiling alcohol afford Icevulic acid ketazine, C10H 16O4N2, m. p. 119— 120° (corr.). L s e v u lh y d r a z id e
an d hydrazine hy d rate give Imvulhydrazide ketazine, C10H 20OoN4, m. p. 219—220° (corr.). H. Wr e n.
S tru ctu r es of con v olvu lin olic and japalinolic acid s. S y n th e s is of «-hydroxyperitadecoic and K -hydroxyhexadecoic a cid s. L. A . Da v i e s and R . Ad a m s (J. Amer. Chem. Soc., 1928, 50, 1749 1755).—M ethyl L-aklehydododecoate, b. p. 141—
143°/4 m m ., is converted by- magnesium n-amyl brom ide into methyl K-hydroxyhexadecoate, m. p. 40-5 41-5°, b. p . 183— 186°/3 mm. K-Hydroxyhexadecoic acid, m . p. 68—69°, prepared by hydrolysis of the ester, is oxidised b y chromic aoid in glacial acetic acid to K-kelohexadecoic acid, m. p. 74—75°. Since these acids are obtained also from japalinolic acid b y oxidation and subsequent reduction of the keto- aeid th u s produced, i t follows th a t this acid is d-K- hydroxyhexadecoic acid. Similarly, m ethyl t-alde- hydododecoate an d magnesium ?i-butyl bromide afford methyl K-hydroxypentadecoate, b. p. 166°/2 mm., m. p. 29—32°, from which K-hydroxypentadecoic acid, m. pi 63-5— 64°, an d K-ketopentadecoic acid, m. p. 70 71°, are derived. Convolvulinolic acid has a structure different from th a t of K-hydroxypentadecoic acid.
Q-Ketohexadecoic acid, in. p. 73-5—74-5°, is described.
H . Wr e n.
S y n th e sis of h ep tan e-as-d icarboxylic acid.
A. S. Ca r t e r (J. Amer. Chem. Soc., 1928, 50, 1967—
1970).— Ethyl 8-phenoxypropylmalonate, b. p. 228