Oct., 1943
SOMll ~'ORMi\l,DIlHYD13
DERIV.\TIVFES OF
ICONTKIBUIION F R O M T H B CH13MICAL
A J m r r YLENIC
LABORATORIES O F THE
HYDROCARBONS
1847
UNIVERSlTY OF NOTRE D A M E ]
Some Formaldehyde Derivatives of Acetylenic Hydrocarbons' 13ir G. I;. HENNION AND E. P. I ~ E L L
Introduction l l ' i t l i thc rxccptiori of forinaldeliytle, most &I-
tlehytlcs aiid kctones react readily with sodium acctylides in liquid ammonia to yield the various alkytiyl carhinols.2 Since the alkyipropargyl alcohols arc more difficult to make, especially from paraformaldehyde, we have been interested in synthesizing some of their derivatives by means of metathetic reactions with monomeric methylene compounds. As typical examples of potentially suitable A--CH2---B reagents we investigated reactions of several chloromethyl esters, chloromethyl ethers, methylene bromide and methylene sulfate with sodium acetylide and acetylenic Grignard reagents under a variety of conditions. The chloromethyl esters could be used only in inert organic solvents and gave but poor yields of derivatives of the type K-C==C-CH~--O-The highest yield was 20% of butylCO--R'. propargyl propionate obtained by adding chloromethyl propionate to sodium butylacetylide suspended in toluene. Coating of sodium alkylacetylides with sodium chloride and further condensations of the desired esters likely account for the low yields. N o product was obtained when
Compound
CONSTANTS, YIELDS A N D Yield. B. p.
CIIIV-CC-CHI-C~CO-CH~ CsHn-C~.C-CH?-O-CO-~€I~* C,Hp-C-C-CHr---O-CO-C?Ha C~HI-C~C-CH~O-CO-C~~II G H v - C ~ C - C H ~ ~ O HI'' C C~Hv-C~C-CH~-OC~H~ CIHP-C~C-CH~-OC~H: (CdHr-CTC-CHr-),O (CcHo-CEC-)?C tI?
yo
"C.
Mm.
IH
82-83
7
10 21
79-81
ti
70-71 lli0-162
4
2
80-81
29
77-78 M-62 110-142 1OR-110
20 0
IO 42 27 34 21
13
li 8
sodium acetylide suspensioiis remain relatively coarse and granular. Sodium butylacetylide in ether also remaiiis coarse even after corisiderablc boiling. The reaction of chlorornethyl ethers with acetylenic Grignnrd reagents in ether solution proceeds somewhat better.3 The highest yield was 42yo of butylpropargyl methyl ether from monochlorodimethyl ether and hexynylmagnesium bromide. The ethyl and n-propyl ethers which have been made previously4 by reaction of the Grignard reagent with the formals were also obtained. .4s expected, methylene bromide failed to react with both sodium butylacetylide in liquid ammonia and hexynylmagnesium bromide in ether. I n the former reaction, however, considerable tarry material was obtained. On the other hand, methylene sulfate reacted very slowly with an ether solution of hexynylmagnesium bromide and gave a very low yield of a hydrocarbon, presumably 3,s-tritlecadiyne. The slowness of the reaction may be due to the very limited solubility of methylene sulfate in ether. The various products are described in Table I.
'I'ARLB I ANALYTICALD A T A
N%I
1.4400 1 . 4 4 4 0 0.!UIil 1 . 4 4 3 2 I) !)24ti 1.5175 1.4320 1.4334 I I:W0 1.40fiO 11728
FOR PRODUCTS
Mol. wt. hlK d% Cnlcd. Obs." Calcd. Obs. 1) 9437 I54 153 4 3 . 4 2 4 2 . 0 9
1.0238 U.8403 0.8343
168 168 210
lli3 170
214
126 140
127
0 8Rfi2
I54 200
O.832(;
176
151 207 170
0 R33fi
140
48.01 48.04 48.04 4 8 . 1 6 6 2 . W 63.17 3 8 . 7 9 38.97 43.41 4 3 . 6 S 48.03 4 8 . 3 0 R1.38 64 6 1 5 8 . 2 4 57.84
% Carbon % Hydrogen Cnlcd. Obs. Cslcd. Obs. 70 12 69.!)3 9 . 0 9 9.06 71 . 3 8 71.38 77.77
71.29 71.29 77.36
0,58 9.58 7.40
9.48 9.66 7.42
77.92 81 5 5 88.63
78 02 11.68 8 1 . 4 1 10.67 8 8 . 6 0 11.36
11.81; 10.72
11.23
Cryoscopic in benaenc. Boiling point only reported by Mourcu and Destnots, Compt. r e d . , 132, 1234 (1901). ' On arialysis t\vo separaic samples explodcd and denioli.shcd combustion tubes. a
chloromethyl acetate reactetl with a suspeiision of sodium acetylide in either benzene or ether. In this connection it is interesting to note that sodium butylacetylide arid the higher homologs may be very fixiely dispersed tlirough either l ~ c ' i i zeiie o r toluerie by boiling. : r i i t l stirririg while tlic ( 1 ) l'ayrr SI.VI on siibstitutsd a c v ~ ) l r i i r h . t u 1 1 tlteir ( l c r i \ u i i \ e a , prc\ious ydpcr, 'lttrs JUIIMNAL, 66, 0Oi ( 1!1 I : + ! . 12) ( a ) Caulplwli, Catngbrll arid l ? i > y , i h r d . , 6 0 , L'YXL' I l ! l : < X ) : 11)) I ~ r ~ ~ i and i i g Herinion. ; h i d , , 68, I;::< ~1!141!1, ( c ) Iirltliiori rrud hltirmy, i h i d , 64, 1220 (l!l4!2],
1845
EDNAM. MONTGOMERY, NELSONK. RICHTMYER AND C. S. HUDSON
previously described. Butyl- and amylacetylene were obtained in the usual manner.* Reaction of Chloromethyl Acetate with Sodium Butylacety1ide.-Twelve grams of sodium (0.5mole) was converted to the amide in 800 cc. of liquid ammoniaQcontained in a 2-liter three-necked 5ask provided with condenser, mercury-sealed stirrer and dropping funnel. Butylacetylene, 41 g. (0.5mole), was added dropwise and the ammonia allowed to evaporate through the (dry)condenser and a soda-lime tower. When nearly dry, 500 cc. of anhydrous benzene was added. Dry nitrogen was passed through the flask with vigorous stirring and refluxing for about six hours. After cooling, 54 g. (0.5mole) of chloromethyl acetate, diluted with an equal volume of dry benzene, was added dropwise. The mixture was then refluxed with stirring for one and one-half hours, cooled and poured into ice-water. The organic layer was washed until neutral to litmus, dried over magnesium sulfate and fractionally distilled. The ester was put through a Whitmore-Fenske column and then redistilled through a modified Podbielniak column, both under vacuum. The yield was 12.7 g. or 16%. When repeated with bromomethyl acetate in ether the yield dropped to 9.7'3,. Saponihation equivalent calculated for butylpropargyl acetate, CH&OOC?Hl,, 154; obs., 155.9. Reaction of sym-Dichloromethyl Ether with Hergnylmagnesium Bromide.-One mole of magnesium tuinings was converted to the Grignard reagent with ethyl bromide in the usual manner. Eighty-two grams of butylacetylene diluted with a n equal volume of dry ether was added (8) Vaughn, Hennion. Vogt and Nieuwland. J . Org. Chcm., 2, 1 (1937). (9) Vaughn, Vogt and Nieuwland. (1934).
[CONTRIBUTION FROM
THE
THISJOURNAL, 66,
2120
VOl. 63
slowly and the mixture refluxed until the evolution of ethane ceased. About 0.1 g. of cuprous chloride was introduced1° and 57 g. (0.5mole) of sym-dichloromethyl ether (diluted with ether) added slowly. After heating for onehalf hour and standing overnight, the product was hydrolyzed with ice and acetic acid. The dibutylpropargyl ether was purified as described above. The yield was 22.3 g. or 21%. Reaction of Methylene Sulfate with Hexynylmagnesium Bromide.-Approximately 0.5 mole of butylacetylene Grignard reagent was prepared as noted above. About 0.1 g. of cuprous chloride was added to the mixture and 55 g. (0.5mole) of methylene sulfate extracted into it. This was achieved by placing the solid sulfate in a Soxhlet type extractor and refluxing the solvent ether through it. Complete extraction took about fifty-six hours and a t the end of this time the mixture was decomposed with ice and hydrochloric acid. The layers were separated, the aqueous layer extracted with ether and the extracts combined with the organic layer. This was washed, dried and the ether distilled off. The small amount of residue was fractionated twice through a 50 cc. Claisen flask with small Vigreux column. The yield was 5.9 g. or 13% of 5,stridecadiyne.
Summary Sodium alkylacetylides and the corresponding Grignard reagents have been treated with a number of formaldehyde derivatives to yield various alkylpropargyl compounds. Nine products are described. (10) Danehy, Killian and Nieuwland, ibid., 58, 611 (1936).
NOTREDAME,INDIANA
RECEIVED JUNE 1, 1943
DIVISIONOF CHEMISTRY, NATIONAL INSTITUTE OF HEALTH,u. s. PUBLIC HEALTH SERVICE]
The Alkaline Degradation of Phenyl-p-lactoside, Phenyl-8-cellobioside and PhenylD-gluco-p-D-gulo-heptoside BY EDNA M. MONTGOMERY, NELSONK. RICHTMYER AND C. S. HUDSON In an earlier paper1 i t was shown that phenyl-& D-glucoside and phenyl-8-D-galactoside are degraded readily by the action of hot, aqueous potassium hydroxide to D-glucosan < 1,5>j3 C 1,6> and D-galactosan < 1,5> /3 < 1,6>, respectively, whereas the corresponding anomeric phenyl- ahexosides are attacked only very slowly, if a t all, under considerably more drastic conditions. It was suggested that the diffeiences in reactivity might be used as a basis for determining the configuration of the glycosidic carbon atom in these compounds, and in the other anomeric glycosides and sugars with which they may be correlated. (1) Montgoniery, Richtmyer and Hudsod, THISJ O U R N A L , 66, 3 (18.13).
Karrer and Smirnoff2found that acetobromo-aD-glUCOSe will add trimethylamine, and that the resulting tetraacetyl-D-glucosido-trimethylammonium bromide is cleaved readily by hot alkali to form D-glucosan < 1,5> p< 1,6> ; the other products are trimethylamine, acetic acid and hydrobromic acid. If the quaternary ammonium halide has the @-configuration,as Michee13 has suggested on the basis of its low rotation, the formation of levoglucosan in the two types of degradation may proceed through similar (2) Karrer and Smirnoff, Ilcil'. ( ' h i w . A r l u . 4, 817 (1Y%l). (3) Micheel, Bcr., 62, 688 (1!12I,b), hliclirel and Ivlicheel, i b i d . . 63, 386 (1930). (4) See Micheel and Uichrel, i b i d . , 63, %ti2 (1930); 68, 258 (1932), for additional infortnation iu regard to possible mechanisms.
