DECEMBER
1957
g. (2173, m.p. 115-130". Another crystallization gave a melting point of 128-131", undepressed by admixture with authentic 1,2-dihydronaphthalene picrate.
Acknowledgments. Microanalyses are from the Institutes service analytical laboratory directed by Dr. William C. Alford, and infrared and ultraviolet spectra determinations are by Mr. William M. Jones and Mrs. Anne H. Wright, respectively. LABORATORY OF CHEMISTRY NATIONAL INSTITUTES OF HEALTH 14,MD. BETHESDA
Organic Deuterium Compounds.
I. 1,2-Dimethoxy-dc-ethane-d4 and 2-Methoxy-d~-ethan-d4-o11 EUGENE R. BISSELLAND ROBERTE. SPENGER
1713
NOTES
The isotopic purity of the deuterium oxide used was 99.6oJ, and that of the ethylene-dr better than 99%. EXPERIMENTAL'
Ethylene-& glycol. Ethylene-d, was brominated in carbon tetrachloride solution at 0". Distillation yielded 47.8 g. of 1.53367 (Lit.* b.p. 129.5', dibromide b.p. 128-131", n$' n y 1.5360). The dibromide was converted in 78.5% yield to ethylene-dc glycol by the procedure of Bannard, Morse, and Leitch.2 B.p. 113-115"/12 mm., n y 1.42831 ( L k 2 b.p. 86-87"/8 mm., n'," 1.4293). Acetic-da m'd-d. Diacetyltartaric anhydrides was pyrolyzed according to the procedure of Hurd and Pilgrim4 t o afford an average yield of 42% of carbon suboxide, b.p. 7-8'. This was converted via malonic-dz acid-dz to acetic-ds acid-d in 89-97% yield by the method of Wilson.6 d26 1.137, nz 5 . 1 1.3675. MethyGds bromide. Silver acetate-ds, prepared from aceticd3 acid-d by the method of Nolin and Leitch,e was subjected to the Hunsdiecker degradation in an apparatus (Fig. 1)
Received April 29, 1957
I n connection with some nuclear magnetic resonance studies being conducted in this laboratory, a a need arose for a material with the solvent properties of ethylene glycol dimethyl ether (1,2-dimethoxyethane) which would, however, show little or no I1I111 nuclear magnetic resonance signal in the proton region. Since a completely deuterated ethylene glycol dimethyl ether would meet these requirements, we undertook its synthesis starting with deuterium oxide and a sample of ethylene-do available to us. Ethylene-dr was converted via its dibromide to ethylene-dr glycol diacetate which was then hydrolized to the free glycol.2 The glycol thus obtained was converted via its monosodium derivative to a 2-methoxymixture of 1,2-dimethoxy-d6-ethane-d4, ~. -Fritted dlsk d3-ethan-d4-ol, and unchanged glycol by treatment with methyl-d3 bromide. The 2-methoxy-da-glycol could be further methylated to the diether. The methyl-ds bromide was prepared from carbon suboxideas4via malonic-dz acid-dz and acetic-dt a ~ i d - d . ~ The procedure of Nolin and Leitch6 for the HunsFIGURE 1 diecker degradation was modified to eliminate the somewhat hazardous sealed tube operation. consisting of a trap (A) connected to a vacuum system, a Comparison of the nuclear magnetic resonance mercury bubbler (B) containing about 0.5 inch of mercury, spectrum in the proton region of the 1,2-dimethoxy- and a reaction tube (C) charged with 20-40 g. of silver ds-ethane-dr, obtained by this method, with that of acetate-d3. Attached to the bottom of the reaction tube was bromine reservoir (D) containing about 25 g. of %mesh normal material indicated that the isotopic purity aDrierite and bromine in about 2% excess over that required of our deuterated material was a t least 98.6 and to consume all of the silver acetate-d3 in C. After assembly of the apparatus with the center tube in the probably better than 99 atom per cent deuterium.
I
M
bubbler (B) raised with a magnet from the outside, the bro(1) This work was performed under the auspices of the mine reservoir was cooled to -78", and the system was U. S. Atomic Energy Commission, Contract No. W-7405- evacuated. The trap (A) was cooled in liquid nitrogen, and eng-48. argon was admitted to the system to a pressure of 150 mm. (2) R. A. Bannard, A. T. Morse, and L. C. Leitch, Can. The argon served to control the rate of flow of bromine vapor J . Chem., 31,351(1953). through the silver acetate-ds bed. The center tube in B was (3) A. Wohl and C. Oesterlin, Ber., 34, 1139 (1901). lowered and the bromine reservoir allowed to warm to room (4) C. D. Hurd and F. D. Pilgrim, J . Am. Chew. SOC., temperature. During the first hour or so of the reaction pe55,757 (1933). (5) C.L. Wilson, J. Chem. Soc., 1,492 (1935). (7) Boiling points are uncorrected. (6)B. Nolin and L. C. Leitch, Can. J . Chem., 31, 153 (8) L. C. Leitch and A. T. Morse, Can. J . Chem., 30, (1953). 924 (1952).
1714
NOTES
VOL.
22
riod, the pressure rose to about 200 mm. The argon was care- 34 mm. a t 12", 18 mm. a t 0", 3 mm. a t -23", and about 1 fully bled off to maintain the pressure a t about 150 mm. mm. a t -41". A 0.25-mole run could be completed in 12-16 hr. When all I,&Dimethoxy-d6-ethane-dr from 2-methoxy-d3-ethan-d4-01. of the silver salt had turned a bright yellow and bromine 2-Methoxy-da-ethan-dol (1.44 g., 0.017 mole) was treated vapor was visible in the Pyrex wool plug and in the space with 0.40 g. (0.017 mole) of sodium and 17.4 millimoles of above it, the system was evacuated very slowly (about 5 methyl-dy bromide using the procedure described above. mm. per minute). When the pressure in the vacuum system There was obtained 0.9 millimole of material volatile at had dropped to less than loop, the center tube in B was raised -96". The material from the -96" trap was dried over bit a t a time until clear of the mercury; the systen was then sodium and distilled on the vacuum line to yield 1.46 g. *?vacuatedto a hard vacuum (< 1 p pressure). If bromine was (85%) of 1,2-dimethoxy-de-ethane-d4. apparent in trap A, its contents were repeatedly passed Acknowledgments. The authors are indebted to through the mercury bubbler from trap A to reservoir D and back until all color had been removed. The center tube of B Dr. Melvin P. Klein for the nuclear magnetic resowas raised to allow free passage on the A to D portion of the nance measurements and to Drs. John W. Nury, cycle and lowered on the D to A portion. The stopcock on the sidearm of trap A was closed and the contents of the trap Bert E. Holder, and Melvin P. Klein for suggestion distilled through two U-traps at -96" and a t - 130", respec- of the problem. tively. Any material passing through the -130' trap (mostly UNIVERSITY OF CALIFORNIA RADIATION LABORATORY (201)was discarded. The methyl-dr bromide in the -130" LIVERMORE SITE trap was measured gasometrically and transferredto a storage LIVERMORE, CALIF. bulb. The material in the -96" trap (presumably acetic-da acid-d and acetyl-da bromide) amounted to about 50 mg./g. of silver salt and had a density of 1.1 g./ml. and a vapor pressure of 20 mm. a t 0". It was not investigated further. The Preparation of a-Morpholinoacrylonitrile average yield of methyl-d3 bromide was 78%. Its vapor pressure at -41" and at 0" was 81 mm. and 680 mm., respecSAMUEL C. TEMIN tively ( N o h and Leitche give 681.5 mm. a t 0"). I ,2-Dimthoxy-d6-ethne-da and 2-methozy-d3-ethan-d4-01. A reaction tube of about 200-ml. capacity, fitted with a Received April 82, 1957 breakseal and a neck constricted for sealing under vacuum, was loaded in a dry box with 2.30 g. (0.10 mole) of sodium. I n connection with a study of vinyl monomers The reaction tube was then attached to a Dry Ice condenser containing a basic substituent it became desirable having a side arm for the introduction of other reactants and protected from moisture with an ascarite filled drying tube. to synthesize the title compound. The literature] Approximately 50 rnl. of sodium-dried liquid ammonia was reveals but one preparation of a-(substituted amdistilled into the reaction tube from a flask attached by means of an adapter to the side arm of the condenser. The ino)-acrylonitriles; this procedure involves the use flask and adapter were then removed, and the side arm was of liquid HCN and more than two moles of secondcapped with a rubber syringe stopper through which 6.61 ary amine. g. (0.10 mole) of et.hylene-dd glycol was slowly introduced 2 RiNH by means of a hypodermic syringe and long needle. The ClCHzCHO MCN --+ ClCH&H(OH)CN reaction tube was maintained at -35" to -40" during the CHFCC~JRZ)CN RzNH*HCl (I) addition. When the addition of the glycol was complete the syringe wz,s washed Lhree times with 10-ml. portions, of so- We have found that the previously unreported I, dium-dried ether. i f much unreacted sodium remained caked (Rz = GHsO), can be prepared in fair yields by an on the ~ v d hof the tube, the syringe was replaced by a stainless-steel wire and the solids chipped off the glass. The improved procedure which (a) avoids the use of apparatus was tbert dlowed t o warm slowly to room tem- liquid HCN, (b) substitutes caustic for an excess of pera,ture overnight to allow the ammonia and some of the the more expensive amine, and ( c ) permits the whole i ? t h $0 evapors.te. The last traces of ammonia and ether operation to be performed in one flask without the and ahout 0.1 g, OF mrea,cted glycol were removed by baking isolation of intermediates. Dimethyl chloroacetal is the re&ion t abe 3';IOO" under hard vacuum (:c 1p pressure) +ds bromide (0.10 mole, measured gaso- hydrolyzed with dilute mineral acid to the free aliled into the Cube which was theu sealed dehyde. To the resultant solution is added an aqueoff a.t the constriction. After 10 days a t mom temperature, the ous solution of the amine hydrochoride and: after reaction tub- ww attaohed via its breakseal to a series of coolirig, sodium cyanide to form the P-chloroaminolint.? :md the volatile components of its nitrile. Dehydrochlorination, to give the title ntcl the first trap. The last traces were tion vessel by heating it at 100" for compound, is accomplished by addition of one 1% of noncondensible material was equivalent of sodium hydroxide. The technique is puryetE oE. A ppr.,xima,b!y 1-2 millimoles of volatile ma- a,pplicable to other secondary amines. t e ~ J hwas rernnverl from +,he matmial in the trap by disThe product was unstable and decomposed on p it through B -96" trap. The liquid residues from two mfibzbined and fractionated through standing a t room temperature even in the dark. c o h m t;o yield 0.93 g. of forerun; 3$ ny.2 1.87644; 5.05 g. of 1,2-diEXPERIMENTAL^ .p. 83-84."; 0.49 g. of an intermediate cut,, b.p, :l.5-.L2io, dZj.g 0.993. n 2 ~ . c1.38572; ' 4.38 e;. To 63 g. (0.5 mole) of dimethyl chloroacetal (Carbide and b.p. 1";%-12,4", dm.5 1..042,?LY"' @a,rbon Chemicai Go.) was added 80 ml. of 0.75N hydroua,l ethylen,d.i glycol. Ths i.,% ; I ) 0.Kicndemus, H. Langc, and H. BTranz, U.S. Patent drjwi over frestriir cut sodii~m 2,291,152 (Lo General Aniline and Film Gorp.) August 13, 1931 lr pressures at, the t (2) Mslting points si xxorrected. ' Ci;i snm.&it 23.9". fb
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