CHARLES D. HURDAND DONALD G. BOTTERUN
1200
VOl. 68
colorless oil, h. p . 92--95" ( 5 0 m m . ) . This representsa 5fi(,% over-all yield from 5-methylfurfural. Calcd. for CxH1,SO: X, 9.8. Found: N,9.6. (€3) Twenty-five grams of N-ethyl-5-methylfurfurylamine, prepared a s described previously, was hydrogenated using 2 g. of Raney nickel catalyst and an initial hydrogen pressure of 1800 Ih. Distillation of the product yielded 23 g. (90%) of colorless oil, b. p. 67-70" (20 nim.). Calcd. for CsHI,S0: S , 9.8. Found: s, 9.8. A purified sample of the tetrahydro amiiie had the physical constants: nZsu 1.4387; d2j4 0.887.
N-Ethyl-5-methyltetrahydrofurfurylamine Hy-
11.
1.
drochloride.-The halt was prepared as des:.riljcd previously. I t crystallized as buff platri from acetone, in. p . , 98-99', Ana!. Calcd. for C & j N O C l : S , 7.8; CI, 1 9 3 . Found: S, 7.7; C1, 19.6. N-Ethyl-N-5-methyltetrahydrofurfuryl3,s Dinitrobenzamide.-The :3,j-dinitrobenzcatPs of both the amines from (A) and ( B ) , prepared according to Shriner and Fuson,' separated as colorless needles from alcohol. The n i e l t i n ~ points from ( A ) : 89-89.5"; from (€3) 87-88"; a mixture of the two, 87-88". Anal. Calctl. for CI,H19S.i04: S , 12.5, Found: S , from (A), 12.0; from i B ) , 12.2.
5-.blethylfurfural (IV) was condensed with ethylamine to give the imino (V) derivative. Reduction of V with hydrogen and Kaney nickel Summary gave N-ethyl 5-methyltetrahydrofurfurylamine (VI) in Xi(& over-all yield. The crystalline 3 , 3 The synthesis of seventeen new furfuryl amines dinitrabenzoate (111),of V I was identical with has been accomplished by condensing 2-methylthat prepared from 11. furan with formaldehyde and various substituted N-Ethyl-5-methyltetrahydrofurfurylamine.--(A) 5- ammonium chlorides. The reaction takes place ~iiethylfurfiiral~ (51.8g., 0.45 mole) and 04.3 g. (O.4T mole) a t the free alpha position on the furan nucleus. of :33(%Et"* were mixed with cooling in a 200-cc. ErlenThe structure of these compounds has been nicycr flask. After the strong heating had subsided t h e reaction was allowed t o stand a t room temperature for one demonstrated in one instance by the identity of hour with occasional shaking. At t h e end of this time t h e the properties and mixed melting point of the upper organic layer was separated and washed once with product with those of a sample prepared by an 1uc) c c of water. alternative and unambiguous method. Thc: crude imine was hydrogenated directly, using 4 g. of Raney hickel catalyst and a n initial hydrogen pressure of 1700 Ib. Distillation of t h e product gave 43.8 g. of (3) liinkes, "Organic Syntheses," Coll. Vol. 11, John Wile?. and Sons, Inc:, N e w Y o r k , S . Y . , 1'348,11. 393.
(4) Shriner and Fuson " T h e Systematic Identification o f Organic Cornpound'." John U r l e y aud S o n s , I n c . , N e w York. N . Y . , 1040, p . 117.
RECEIVED MARCH 1, 19-E
AMES,IOXA
[ C O N T K I I ~ U III J Y F R ( I M 1 I l l < C I I E M I C A I . ~ . A I I O R A ' T O I I Y O F ~ O K T I I \ V E S Il i K S [JZIIVL'KSIT\
1
Vinyl Ethyl Ether and Other Vinyl Ethers B Y CHARLES D. HURDAND DONALD G. BOTTERON' The preparation of vinyl ethers by the action of solid potassium hydroxide on 2-bromoethyl alkyl ethers is known, illustrations2 being vinyl allyl ether and vinyl y-ethylallyl ether. No such synthesis of simple vinyl alkyl ethers from 1chloroethyl alkyl ethers has been reported, however, although 2,2-dichlorovinyl ethyl ether has been prepared from ethyl 1,2,2-trichloroethyl (1) Research associate, 1041-1043. This investigation was s i ~ o n sored h y Pittsburgh Plate Glass Company. ('2) Hurd and Pollack, T I I I S J O U R N A L , 60, 1905 (1038); J. OVi. C h e m 3, 550 (1939).
ether by the action of heat3 and by the action of 5056 potassium hydroxide. When niixetl with pyridine and distilled, 1chloroethyl ethyl ether yielded vinyl ethyl ether: CH3CHClOC2Hb C5H5N --+ CHz-CHOCpHs C6HsNHC1. No vinyl ethyl ether was obtained when solid potassium hydroxide, solid sodium hydroxide, dibutylamine, or dimethylaniline was used as the base. Hydrolysis was en-
+
+
(3) Oddc and hfarneli, C u m ~ h i i i~f n~i ,. 33, 11, 3 i 3 ( 1 9 0 4 ) ; C h e m . Zciili, , TI, I , 1)20 (19LI-l) ( 4 ) C o d e f r o s . i o i n p t . r e u d . , 102, 869 (188Ci).
July, 1946
VINYLETHYL ETHERAND OTHERVINYLETHERS
countered when the solid hydroxides were used since both ethyl alcohol and acetaldehyde were obtained together with unchanged chloro ether. Attempts t o adapt this reaction t o the bis-1chloroethyl ethers of ethylene glycol or diethylene glycol gave none of the anticipated vinyl ethers. In these cases, bases promoted acetal formation, ethylene acetal being obtained in is70 yield 'by reaction of ethanediol bis-1-chloroethyl ether with pyridine, and 3-oxapentaniethylene acelral (or 2-niethyl-l,3,6-trioxacyclooctane) being formed by heating a mixture of 2-( 1-ch1oroethoxy)ethyl ether and quinoline. Two experiments were performed with vinyl 2-hydroxyethyl ether. The first was hydr0gen.ation. The vinyl ether hydrogenated readily in the presence of a platinum catalyst, yielding cellosolve. In the second experiment the coinpound, in the form of its sodium derivative, underwent reaction with allyl bromide to yield vinyl 2-allyloxyethyl ether, CHpCHCH20CH2CH2OCH=CH*.
Experimental 1-Chloroethyl ethyl ether was prepared from paraltlehydc, ethanol and hydrogen ~ h l o r i d e . ~ Viiiyl 2-hydrox.yethyl ethcr was obtained by reaction of sodium on ethylene brornoacetal.6 Vinyl Ethyl Ether.-Twenty-fcur grains (0.22 niolc) of I-chlorcethyl cthyl ether was added to 40 ml. ( 0 . 5 mole) of pyridine a t room tcmpcrature. From the niixturc was obtained 14 nil. of distillate bcfore the vapor tetnpcrztvxe reached 100". This was redistilled through a 12-cm. Vigreux column t o yield 6.8 g. (0.1 mole, 43y0) of vinyl cthyl ether, b. p . 335-40°, n Z 11.3737. ~ Values reportcd7 for carefully purified material: b. p. 35.72 and ~ ? O D 1.37fi8. Wislicenuss found t h a t ethyl vinyl ether polyriierizcs in the presence of iodine. Our material was feud t o react vigorously when added to a crystal of iodine. Ethanediol Bis-1-chloroethyl Ether.--A mixture of 80 i i i l . cf paraldchyde and 1 2 ml. of ethyleiie glycol \\as iaturared with dry hydrogen chloride a t 0'. The upper layer was dried over sodium sulfate, then fourteen hours at -10" over tlrierite. and then was distilled. The Dortion boiling above 8 9 (20 nim.) was redistilled; yield, 25.2 g. (185Cj of b. p. 92-94" ( I 5 mm.), n 2 0 ~1.4498, density 1.149 at 23.5'. Anul. Calcd. for CsHlrCLOz: C1, 38.0. F O L I I I ~(!l,: 35.3. Reaction with Pyridine.-A mixture of 23 p. of thc ether and 24 ml. of pyridine was distilled. Most of the distillate (12,x g,) collectetl j()-.yso leaving a of pyridine hydrochloridc in t h e flask. Kedistillatioti yicltled 9.2 g. (78%, yield) of ethylene acetal, b. p. 82-85",
-
( 5 ) Henze a n d hfurchison, THIS JOURNAL. 53, 1077 (1931). (ti) Hill and Pidxeon, ibid.. 60, 2718 (l!l28). (7) Dolliver. Gresham, I
