Debromination of Pentaerythrityl Bromide by Zinc. Isolation of Spiropentane

M. J . M u rray a n d E . H . S tevenson. J . Amer. chem. Soc., 1944, 66, 812-816.— A R a m a n spectroscopic in v estig a tio n of th e p ro d u c ts o b tain e d fro m re d u ctio n of p e n ta ­ e ry th rity l b rom ide b y zinc in aq u eo u s m eth a n o l show ed tw o R a m a n lines n o t assig n ­ ab le to e ith e r th e m a in p ro d u c t, m ethyleneeycfobutane, o r to 2 -m ethyl-1-butene. A m ix tu re co n ta in in g a larg e r p ro p o rtio n of th is th ir d co m p o u n d w as o b tain e d b y re d u c tio n of p e n ta e ry th rity l Jjrom ide w ith zinc in m o lten acetam id e in th e presence of sodium c a rb o n a te a n d sodium iodide. T h e new com pound w as iso lated b y rem oval of th e olefins w ith a q u eo u s so lutions of silver salts a n d w ith brom ine. T h e possible id e n tity of th e co m p o u n d is discussed, a n d in th is p re lim in a ry s tu d y th e belief is expressed t h a t th e iso latio n of sp iro p e n ta n e h a s b een effected. E . H . W . 100. Reaction of Benzene with Butadiene in the Presence of Sulphuric Acid and Hydrogen Fluoride Catalysts, v . N . Ip a tieff, H . P ines, a n d R . E . S chaad. J . Amer. chem. Soc., 1944, 66, 816-817.— A s tu d y h a s been m ad e o f th e re a c tio n of b u tad ie n e a n d excess benzene w ith su lp h u ric a cid o r h y d ro g e n fluoride a s c ata ly sts . I n th e presence of su lp h u ric acid, a p p ro x im a te ly 1-5 m oles of benzene re ac te d w ith 1 m ole of b u tad ien e giving a 14% y ield (based on benzene w h ich re ac te d ) o f 1 : 2 -d ip h en y lb u tan e. W ith h y d ro g e n fluoride, a p p ro x im ate ly 1-2 m oles of benzene re ac te d w ith 1 m ole of bu ta d ie n e giv in g a 59% y ield of 1 : 2 -d ip h en y lb u tan e . E . H . W . 101. Viscosity of the Methyl Ester of Dilinoleic Acid. D. W . Y o u n g a n d R . E . Bier- tu em p fel. J . Amer. chem. Soc., 1944, 66, 843-844.— T h e k in em atic viscosity of a p u re sam ple of m e th y l dilin o leate o ver th e ran g e —40° C. to 100° C. is re p o rte d . T h e in te re s t of th ese resu lts is d u e to th e r a rity of th e p u re m a te ria l, a n d th e fa c t t h a t th e dim er h as a visco sity in d ex (D ean a n d D a v is system ) of 123-0. E . H . W . 102. n-Nonatriacontane. E. S te n h ag e n a n d B. T ag stro m . J . Amer. chem. Soc., 1944, 66, 845-846.— T h e p re p a ra tio n a n d isolatio n of n -n o n a tria c o n ta n e a re re p o rte d . A n X -ra y s tu d y of th e c ry stals of th is new c o m p o u n d w as m ad e, a n d it w as show n to

e x h ib it dim orphism . E . H . W .

103. Zinc Alkyls from Secondary Alkyl Halides. H . Soroos a n d M. M organa. J . Amer.

chem. Soc., 1944, 66, 893-894.— D ifsopropyl zinc a n d d i-s-b u ty l zinc h av e been p re ­ p a re d w ith good yields, b y a d d in g a m ix tu re of th e seco n d ary a lk y l bro m id e a n d iodide slow ly w ith stirrin g , u n d e r c o n tro lled te m p e ra tu re conditions, to a n excess of zin c-co p p er couple. T h e re a c tio n m ix tu re is th e n distilled u n d e r as low a te m p e ra tu re

a n d p ressure a s possible. * E . H . W .

3 2 a A B S T R A C T S .

-dacen e is d escribed. 1 : 4 -d ieth y l-n ap h th ale n e h a s b e en sy n th e size d b y a new m eth o d .

A p ro p o sed m ech an ism fo r th e J a c o b se n re a rra n g e m e n t is discussed. E . H . W . 108. Mechanism oi Peroxide Initiated Styrene Polymerization. H . F. P fa n n , D. J . S alley, a n d H . M ark, J . Amer. chem. Soc., 1944, 66, 983-985.— H alo g en -co n tain in g p o ly m ers h a v e b e en p re p are d fro m sty re n e a n d v a rio u s a m o u n ts of m -brom obenzyl pero x id e in th e liq u id p h a se a t v a rio u s te m p e ra tu re s . T h e b ro m in e c o n te n ts of th e jp o ly m e rs w ere d e te rm in e d g ra v im etriea lly a n d also b y u sin g a rad io a ctiv e brom ine

isotope.

T h e p o ly m ers c o n ta in ed on th e a v erag e b etw een one a n d th re e b ro m in e a to m s per ch ain , if th e visco sity av erag e c h ain le n g th w as co m p ared w ith th e a n a ly tic a l brom ine

co n te n t, E . H . W .

109. Rearrangement of Alkyl Halides. F . R . M ayo a n d A. A. D olnick. J . Amer.

chem. Soc., 1944, 66, 985-990.— T h e liq u id p h a se re arra n g e m en t of n o rm al a n d iso­

p ro p y l brom ides to a n eq u ilib riu m m ix tu re , a n d th e effect of v ario u s c a ta ly sts a n d in h ib ito rs h a v e b een stu d ied . F ro m analogues b etw ee n th is re a c tio n a n d th e a d d itio n of h y d ro g e n b ro m id e to alkenes, re a c tio n m echanism s h a v e been suggested. E x p e ri­

m e n ts w ere also m ad e w ith i- a n d Z-butyl chlorides a n d th e tw o dibrom oethanes.

P re v io u s w o rk on th e s u b je c t is review ed a n d c o rre late d w ith th e re su lts now

o b tain ed . E . H . W .

110. Alkyl Sulphites—cyclo H ex yl Sulphite. L. P . K y rid es. J . Amer. chem. Soc., 1944, 66, 1006-1007.— T h e p re p a ra tio n of a lk y l su lp h ite s b y th e re ac tio n of p rim a ry a n d seco n d ary alcohols w ith th io n y l chloride a t low pressures is described.

ci/cloHexyl su lp h ite m ad e b y th is m eth o d is a re la tiv e ly sta b le p ro d u c t, a n d c an be red istille d re p ea te d ly w ith o u t c hange in com position. E . H . W . 111.* a-Methylenie Reactivity in Oleflnie Systems. Part I. The Prins Reaction with Propylene, j . W . B ak er. J . chem. Soc., 1944, 296-301.— P ro p y le n e re ac ts w ith p a rafo rm a ld e h y d e in th e presence of a m ix tu re of 100% ace tic a n d sulp h u ric acids a t 35° to give : (1) th e d ia e e ta te of » -b u ta n e -1 : 3-diol (63-5% ), (2) th e cyclic fo rm al (14% ) o f th is diol, a n d (3) 4 -a c e to x y te tra h y d ro -y -p y ra n (22-5% ). T h e r a te of a b so rp ­ tio n of each of th e re a c tio n in g red ien ts d u rin g th e course of th e re ac tio n h a s been d eterm in ed , a n d m ech an ism s fo r th e fo rm atio n of th e p ro d u c ts a re suggested on th e

basis of th ese resu lts. C. F . M.

112.* The Action of Aluminium Chloride on Some Phenyl Ethers. G. B addeley.

J . chem. Soc., 1944, 330-332.— T h e a lk y la tio n of th e p h en o l nucleus is show n to be exclusively in th e p -p o sitio n in th e presence of a lu m in iu m chloride, w hereas t h a t of th e phen o l hom ologues is d irected b y th e a lk y l g ro u p s p re se n t in th e nucleus. E th v la tio n occurs m ore re ad ily t h a n m e th y la tio n , a n d th e p ro d u c ts of th e fo rm er a re v e ry re ad ily

isom erized. C. F . M.

113.* The Metal-catalysed Reaction between Acetylene and Hydrogen. Part I.

Nickel Catalysts. J . S h erid an . J . chem. Soc., 1944, 373-380.— T h e r a te of fall in to ta l p ressure in h y d rogen—ace ty len e m ix tu re ^ o ver nickel-pum ice c a ta ly sts increases, u n d e r c o n sta n t conditions, d u rin g th e e a rly stag es of use of th e c ataly sts . T h e y ields of eth y len e, eth a n e, a n d h ig h er h y d ro c arb o n s, e xpressed in te rm s of th e acety len e n o t recovered, a re th e sam e o n fresh a n d old c ata ly sts . T h e course of re ac tio n in 1 : 1 a n d 2 : 1 h y d ro g en : acety len e m ix tu re s o n c a ta ly sts of c o n s ta n t a c tiv ity is p lo tte d . E th y le n e is p ro d u ced a t a b o u t 5 tim es th e r a te of e th a n e fo rm atio n u n til m o st of th e ace ty le n e is rem oved. T h e p ro d u c ts o th e r th a n C2 h y d ro c arb o n s h a v e a n em pirical gross com position of a b o u t C4H „ a n d are form ed in y ields of 5 5 -6 0 % of th e acetylene n o t recovered a t all stag es of re ac tio n , w ith b o th gas ratio s. T h e in itia l re ac tio n on ca ta ly sts of c o n s ta n t a c tiv ity is of first o rd er w ith resp ect to h y d ro g e n a n d of a p p ro x i­

m a te ly zero o rd e r w ith re sp ect to acetylene. T h e h y d ro g e n atio n to e th y le n e a n d th e fo rm atio n of red u ced p olym ers of acety len e b o th h a v e k in etics of a p p ro x im a te ly th is ty p e , b u t differing slig h tly su ch t h a t a n increase from 1 : 8 to 8 : 1 in in itial h y d ro g en : acety len e ra tio causes a n increase from a b o u t 40% to 67% in th e y ield of

D

i r r _ " R A C T S . 3 3 a

3 4 a A B S T R A C T S .

C2 h y d ro c arb o n s, ex p ressed in te rm s of th e ace ty le n e n o t recovered. E t y ene to th e sy ste m a c ts p rin c ip a lly as a n in e rt d ilu e n t, a n d is a p p a re n tly ess ® a d so rb e d t h a n acety len e o n n ickel. T h e sam e c a ta ly s ts h a v e neg gi 6 ac ace ty le n e alone u n d e r c o n d itio n s of ra p id re a c tio n in acety len e—h y d ro g e n m ix • T h e re su lts a re discussed w ith special reference to p re v io u s w o rk o n th e chemiOTrp^i o f eth y le n e a n d acety len e.

114. Absorption Spectra. E . j . B ow en. Progress o f C hem istry A n n u a l R eport fo r 1943, p. 12.— A b rief n o n -m a th e m a tie a l d e sc rip tio n is g iv en of th e re la tio n betw een th e w av e m ech an ical th e o ry of electronic o rb ita ls a n d m o lec u lar a b s o rp tio n sp e c tra of organic su b stan ces. A s a n illu s tra tio n th e a b s o rp tio n sp e c tru m of th e h y d ro g e n m olecule is g iv en in te rm s of th e electro n ic o rb ita l changes. I n sin g le-b o n d ed organic co m p o u n d s th e o rb ita ls a re e sse n tially ag in c h a ra c te r, b u t w h e n a d o u b le b o n d is in tro d u c e d th e e x tr a p a ir of electro n s occupy o rb ita ls in w h ich th e b in d in g is less t h a n in th e a o rb ita ls, so t h a t eth y le n e, fo r ex am p le, a b so rb s a t lo n g er w av e-len g th s t h a n e th a n e f W ith c o n ju g a te d d o u b le-b o n d sy s te m s th e r e is a n in crease in th e n u m b e r of n o d a l p lan e s across th e a x is o f th e m olecule— i.e., th e r e is a n in crease in th e a n ti-b o n d in g electro n s re su ltin g in th e a p p e a ra n c e of m o re a b s o rp tio n b a n d s, th e a b so rp tio n m o v in g to lon g er w a v e-le n g th s. T h is p rin cip le is a p p lie d to th e co n ­ ju g a te d polyenes, a n d it is sh o w n t h a t fo r th e lo n g est w a v e-le n g th of a b so rp tio n th e recip ro cal of th e freq u e n c y s q u a re d is a lm o st a lin e a r fu n c tio n of th e n u m b e r of double b onds.

M eth o d s of c a lcu la tin g th e lo n g est w av e-le n g th of a b s o rp tio n a re a t present- too a p p ro x im a te to b e of d irec t use, th o u g h som e success h a s b e en a ch iev e d in th e ease of th e ben zen e m olecule.

T h e re p la c e m e n t of c a rb o n b y n itro g e n or o x y g e n does n o t g re a tly a lte r th e energy v a lu e s of th e o rb ita ls of th e ty p e m en tio n ed , a n d th e re is th e re fo re little change in th e lig h t a b so rp tio n . T h e o x y g en a to m , h o w ev er, h a s fo u r electro n s o v e r a n d above th o se s h a re d w ith th e c a rb o n in th e C = O lin k . T h ese a re in 2p o rb ita ls, a n d changes in th es e n o n -b o n d in g e le ctro n o rb ita ls a re resp o n sib le fo r th e w e ak k e to n ic a b so rp tio n in th e reg io n of 3000 A.

R e c e n t a tte m p ts to e x p la in th e co lo u r of dyes a re b a se d o n in cre as ed resonance b e tw ee n a lte rn a tiv e electro n ic v a le n cy s tru c tu re s — e.g., th e io n of p -n itro p h e n o l.

0 ^ N—\ x

0 w ~ J . W . H .

115.* Correlating Vapour Pressure and Equilibrium Constant Data. D . F. O thm er.

In d u str. E ngng Chem., 1944, 36 (7), 669.— O n p lo ttin g th e v a p o u r p re ssu re of hexane a g a in s t th e v a p o u r p ressu re of w a te r a t th e sam e te m p e ra tu re , a s tra ig h t-lin e re la tio n ­ sh ip w as o b tain e d , a n d b ecau se of th e ease of w o rk in g w ith th e ta b u la r d a ta fo r w ater, th is su b s ta n c e h a s b e en selected as th e referen ce v a p o u r-p re ss u re s ta n d a rd . I t is sh o w n t h a t on p lo ttin g th e e q u ilib riu m c o n s ta n ts fo r h y d ro c a rb o n s a t c o n s ta n t pressure a g a in s t th e v a p o u r p re ssu re of w a te r a t th e c o rresp o n d in g te m p e ra tu re o n log p a p er a stra ig h t-lin e rela tio n sh ip is o b tain e d . F ro m a series of p lo ts of th is ty p e fo r th e e q u ilib riu m c o n s ta n ts a t differen t pressu res, a n o m o g ra m h a s b een c o n stru c te d w hich p e rm its th e im m e d ia te e v a lu a tio n of th e e q u ilib riu m c o n s ta n t a t a n y te m p e ra tu re a n d p ressu re o ver th e ra n g e 0-5-25 a tm o s. a n d a t te m p e ra tu re s o f 50-400° F . for th e C i-C 8 p araffin h y d ro c arb o n s. A second n o m o g ram is p re s e n te d w h ic h p e rm its th e im m e d ia te e v a lu a tio n of a ll th e e q u ilib riu m c o n s ta n ts for th e co m p o n e n ts of a h y d ro ­ carb o n m ix tu re a t a n y p a rtic u la r te m p e ra tu re a n d p ressu re, th is fo rm of p re s e n ta tio n b ein g v e ry u sefu l in p la te to p la te calcu latio n s. T h e p recise m e th o d of c o n stru c tin g

b o th th e s e n o m o g ram s is described. j j j

116.* Phase Equilibria in the System Ethane-Ethylene-Acetylene. J . L . M cC urdy a n d D . L. K a tz . In d u str. E n g n g Chem., 1944, 36 (7), 674.— T h e p h a se e q u ilib ria in th e ab o v e sy stem s h a v e b e en stu d ie d a t 40° F . a n d 60° F . o v e r th e p re ssu re ra n g e 50-900 p.s.i. T h e follow ing d a ta a re p re se n te d : v a p o u r p ressu res of th e p u re co m ­ p o n e n ts , e x p erim e n tal e q u ilib riu m d a ta fo r th e b in a ry a n d te r n a r y sy stem s, p re s s u re - te m p e ra tu re -c o m p o s itio n d iag ra m s for th e b in a ry a n d te r n a r y sy ste m s a t 40° F . a n d

35 a 60° F . show ing eq u ilib ria a t c o n s ta n t p re ssu re a n d th e com plete p re ssure-com position d ia g ra m a t 40° F . in th e fo rm of a rig h t-tria n g u la r p rism p lo t. T h e c o n stan t-b o ilin g m ix tu re s of e th a n e -a c e ty le n e a n d e th y le n e -a ce ty le n e p e rsist th ro u g h th e tria n g u la r th ree -co m p o n e n t d iag ram s. A t c o n s ta n t te m p e ra tu re a n d p re ssu re th ese d iag ram s h a v e tw o p h a se areas. A cety len e is th e m o st v o latile c o n stitu e n t in one a rea a n d th e

le a st v o latile in th e o th e r a rea. J . W . H .

117.* Determining Fall or Rise Velocity of Spheres in Fluids. R . C. B in d er. Chem.

M etall. E ngng, A u g u st 1944, 51 (8), 104-105.— A c h a r t a n d a se t of fo rm u la are p re sen te d fo r d eterm in in g th e v elo city of spheres in fluids, b a se d o n th e use of th e

B in d er a n d R e y n o ld s n u m b ers. A. H . N.

118.* Viscosity of Normal Pentane. A non. Refiner, A u g u st 1944, 23 (8), 306.— A ta b le is giv en of th e v isc o sity of n -p e n ta n e for te m p e ra tu re s ra n g in g from 25° to 250° C. (inclusive), a n d pressu res ra n g in g fro m s a tu ra tio n pressu res a t 25° C. u p to s a tu ra tio n p ressu re a t 195° C., a n d for o th e r pressures ra n g in g from 100 lb ./sq . in.

u p to 1000 lb ./sq . in . T h e d a ta a re ta k e n fro m th e p a p e r b y H u b b a rd a n d B ro w n w h ich a p p e a re d in In d u stria l and Engineering Chemistry, D ecem ber 1943, 35, N o. 12.

A. I I . N.

119.* Chemistry in Petroleum. J . L. F ra n k lin . Refiner, A u g u st 1944, 23 (8), 3 07- 311.— T h e p a p e r deals in a d esc rip tiv e m a n n e r w ith th e ap p lic atio n of ch em istry to engine design, p e tro l, a n d o th e r p ro d u c ts, special processes in refining a n d synthesis,

a n d g en eral use of p etro le u m in w ar. A. H . N.

120. Chemistry of Catalytic Hydropolymerization of Acetylene. L . I. A n tsu s a n d A. D.

P e tro v . T ra n s la te d b y J . G. T olpin. R efiner, A u g u st 1944, 23 (8), 317-320.— A c e ty ­ lene te tra m e rs of b ra n ch e d -ch a in s tru c tu re w ere o b ta in e d for th e first tim e as p ro d u c ts of p a r tia l h y d ro g e n atio n of acetylene. A m ong th e h y d ro trim e rs of acety len e, th e follow ing olefins w ere fo u n d : 1-hexene, 2-hexene, 3-hexene, 3-m ethyl-1-pentene, 3-m ethyl-2-pentene, 2 -m ethyl-1-pentene, 2 -m ethyl-2-pentene, a n d 2 : 3-dim ethyl-2- b u ten e ; of diolefins, th e follow ing w ere fo u n d : 1 : 5-hexadiene, 3 -m e th y l-l, 4-penta- diene, a n d 2-m ethyl-2 : 4 -pentadiene. T h e p ro d u c ts of ex h au stiv e h y d ro g e n atio n of th ese po ly m ers w ere fo u n d b y R a m a n spectroscopy to c o n ta in n o rm al hexane, 3 -m eth y lp en tan e, a n d 2 -m eth y lp en tan e , a n d b y d e te rm in a tio n of th e in te n s ity of th e a b so rp tio n s p e c tru m lines th e p ro p o rtio n s of th ese h y d ro carb o n s in th e vario u s frac tio n s w ere d eterm in e d . H y d ro te tra m e rs of acety le n e w ere fo u n d to c o n tain 3-ethylhexenes, 2 -m eth y lh ep ten es, 3-m eth y lh ep ten es, a n d 4-m eth y lh ep ten es. T h e a p p ro x im ate c o n te n t of iso-octanes w as d e te rm in ed fro m th e o ctan e n u m b er of th is frac tio n a fte r its e x h a u s tiv e h y d ro g e n atio n . A general o u tlin e of h y d ro p o ly ­ m erizatio n of acety len e over a m ix ed c a ta ly s t (nickel p lu s zinc chloride) is given,

leading to fo rm atio n of di-, tri-, a n d te tram e rs. A. H . N.