Feb., 1949
ALKYL AND CYCLOALKYL CHLORIDES WITH VINYLIDENECHLORIDES
ides, chlorocyclohexane or bromocyclohexane, with ethylene yields the 1- (2-haloethyl)-1-ethylcyclohexanes, the reaction proceeding via the isomerization and subsequent condensation (with a second molecule of ethylene) of the primary product, (2-haloethyl) -cyclohexane. (2,2-Dihaloethyl)-cycloalkanesare obtained by the reaction of vinyl chloride (or bromide) with chlorocyclohexane (or bromocyclohexane) , 1-
[CONTRIBUTION FROM THE
701
chloro-1-methylcyclohexane, and l-chloro-lmethylcyclopentane. A number of apparently new products including 1,l-diethylcyclohexane, 2-( 1-methylcyclohexy1)ethanol and crystalline derivatives, and 1methylcyclohexaneacetyldehyde and crystalline derivatives have been prepared during the characterization of the condensation products. RECEIVED JULY 22, 1948
RIVERSIDE, ILL.
RESEARCH AND DEVELOPMENT LABORATORIES, UNIVERSAL.
OIL PRODUCTS COMPANY]
Condensation of Saturated Halides with Unsaturated Compounds. VI. Condensation of Alkyl and Cycloalkyl Chlorides with Vinylidene Chloride' BY LOUISSCHMERLING The condensation of alkyl chlorides with 1,l-dichloroethylene (i. e., vinylidene chloride) in the presence of metal halide catalysts offers a convenient means for preparing 1,1,l-trichloroalkanes and 1,I-dichloro-1-alkenes. Thus, for example, the ferric chloride catalyzed reaction of t-butyl chloride with the dichloroethylene yields both 1,l,l-trichloro-3,3-dimethylbutane(I) and its dehydrochlorination product, l,l-dichloro-3,3-dimethyl-1-butene (11), the relative amounts of the two products depending on the reaction conditions.
low yield only; the major portion underwent dehydrochlorination to the dichloropentene, the hydrogen chloride adding to the vinylidene chloride to form l,l,l-trichloroethane which was also obtained in 30y0 yield. The structure of the 1,ldichloro-3-methyl-1-butenewas indicated by the fact that it was identical with the product of the the dehydrochlorination of 1,1,2-trichloro-3-methylbutane. The reaction of vinylidene chloride with cyclohexyl chloride in the presence of aluminum chloride proceeded in a similar manner (CH8)sCCl 4-CHz=CCI (CHa),CCH1CCl* to that with isowoDvl chloride. The Feelr ,-. (1) HIO principal product (3b-50% yield) was the dichloroolefin, l,l-dichloro-2(CHs)~CCH2CooH cyclohexylethylene, rather than the tHnO saturated trichloride, 1,l,l-trichloro2-cyclohexylethane. l,l,l-TrichloroKOH (CH3)rCCHClCHCln (CH,)aCCH=CClr ethane was again obtained as byCzH60H product in yield corresponding to the (11) hydrogen chloride evolved during the When the temperature was kept a t -10 to + l o " conversion of the intermediate trichlorocyclo(chiefly at - 10 to O"), a 65% yield of I and a 13% hexylethane to the dichlorocyclohexylethylene. yield of I1 were obtained. At a somewhat higher Hydrolysis of the dichloride yielded cyclohexanetemperature (8-23') the yields were reversed, a acetic acid. 60% yield of I1 and a 14% yield of I being obExperimental tained. Procedures .-The procedures were similar to those preIt is interesting to note that no carbon skeletal described for the condensation of alkyl halides with rearrangement accompanied the formation of the viously haloblefins.2 In Method T, the mixture of reactants and dichlorohexene by the dehydrochlorination of the catalyst in a large test-tube was shaken intermittently a t 1,l,l-trichloro-3,3-dimethylbutane. Confirmation the temperature range shown in the table. In Method S, of the structures of the two products is found in the the mixture of reactants was gradually added t o a stirred fact that each yielded t-butylacetic acid when mixture of the catalyst and n-pentane diluent. heated with water a t 275'. The dichloride was Identification of Products. shown to be identical with that obtained by the I,l,l-Trichloro-3,3-dimethylbutane(I) .-A sealed tube reaction of 1,1,2-trichloro-3,3-dirnethylbutanecontaining 12.5 g. of the trichloride and 150 cc. of water with alcoholic potash. was heated a t 275" for four hours in a rotating autoclavf. The reaction of isopropyl chloride with vinyli- There was obtained 5.5 g. of organic acid, b. p. 1820183 ; 122013 1.4153. It crystallized when coo$!d to 0 . Its dene chloride a t 0-25' in the presence of alumi- fi-phenylphenacyl ester melted a t 92 . t-Butylacetic num chloride resulted in a 30y0 yield of 1,l-dichlo- acid boils a t 183 ', melts ,at 6' and yields a P-phenylphenro-3-methyl-1-butene. The primary product, acyl ester3 melting at 92 l,l,l-trichloro-3-methylbutanewas obtained in __f
-Hcll -
4
.
(1) Preceding paper in this series, THIS JOURNAL, 71, 098 (1949).
(2) L.Schmerling, i b i d . , 68, 1650 (1946). (3) F. Wrede and A. Rothhaas, Bsr., 67, 738
(1934).
LOUISSCHMERLING
702
Vol. 71
TABLE I CONDENSATION OF SATURATED CHLORIDES WITH VINYLIDENE CHLORIDE r
Method
Satd. RCl
ReactantChloride, CHs=CCln.O g. g.
Catalyst MX G.
Temp., OC.
Duration, Chief products hr. Compd. G.
T
t-BuC1
98
93
FeClll
2
-10 to 10
0.8
T
t-BuC1
47
40
FeCI,
1
8to23'
0.5
S
i-PrC1
95
117
AlCI,
gc
1 to 20e
3.0
T
c-CaH11Cl
67
50
AlCli
2
...d
..
I I1 I I1 111 V IV
119 19 11 38
51 48 45
%
Higher boiling prod.,
65 13 14 60 30 30 48
g.
1
1 15
V 21 30 11 IV 64 30 V 48 30 21 0 Obtained from The Dow Chemical Co., redistilled immediately before use. b The catalyst was added to the mixture of reactants cooled to 8' by immersion in an ice-water-bath. The temperature rose to 23" and then dropped to 10' in two minutes. I t was permitted to set a t about this temperature for twenty minutes more, after which it was washed, dried and distilled. The mixture of reactants was added during one and one-half hours to a stirred suspension of 4 g. of aluminum chloride in 62 g. of %-pentanea t 1-3 Additional catalyst (5 g.) was added and the temperature was permitted to rise (stirring continued) to 20' during the next one and one-half hours. d The catalyst was added to the mixture of reactants a t -70" and the temperature was permitted to rise. A sudden reaction occurred a t -20'; the temperature The total reaction time was rose to 35' for a moment and then dropped t o 10' when immersed in the bath a t -78'. three to four minutes.
s
c-CaHnCI
140
114
AlCls
6
0 to20
1.5
.
-
TABLE I1 PROPERTIES OF THE POLYCHLORO PRODUCTS B . p
Compd. I
I1 111
IV V
Formula (CHs)aCCHPCClr (CHi)sCCH=CClr (CHa)sCHCH=CCIz c-CsHiiCH-CClr CHtCClr
B. P.,
OC. 64-65 55-56 50-51 95-96
..,
Mm. 18 39 71 19 ,
.
at 60 mm
.Ci'
166-167 138-139 118-119 204-205 73-74
@OD
1.4608 1.4537 1.4454 1.4948 1.4375
d*o4
1.1644 1.0588 1.0686 1.1236
Mol. Calcd. 44.6 39.2 34.6 46.3
ref. Obs. 44.6 39.1 34.6 46.4
' -Calcd.C 38.00 47.06 43.19 53.63
AnalysesbL% Found-
H
C1 5.85 56.15 6.59 46.35 5.80 51.01 6.76 3 9 . 6 1
C 38.26 46.90 43.21 53.85
H 6.03 6.71 5.84 7.11
'
C1 55.75 46.20 50.92 39.35
Calculated from boiling point under reduced pressure using nomograph prepared for hydrocarbon conversions. This was found to give accurate results for halogenated hydrocarbons. * Microanalyses by Mr. C. W. Beazley, MicroTech Laboratories, Skokie, Illinois. a
1 , l -Dichloro-3,3-dimethyl-l-butene (11).-The hydrolysis of 12 g. of this dichloride was carried out using the same procedure as was used for the trichloride. The sealed tube broke during the heating. The product which was recovered from the autoclave was made alkaline and ether extracted. About 5 g. of unreacted dichloride was recovered from the ether. Acidification of the alkapne solution yielded 1.5 g. of organic acid, m. p."0-5 , the p phenylphenacyl ester of which melted a t 92 There was no depression of the melting point of this ester when it was mixed with the corresponding derivative of the acid derived from l,l,l -trichloro-2,2-dimethylbutane. Further evidence in support of the structure assigned to
.
dichlorodimethylbutene was obtained by showing that the same compound was obtained by the dehydrochlorination of 1,1,2-trichloro3,3-dimethylbutane(prepared by the condensation of t-butyl chloride with cis-dichloroethylener). Fifteen grams (0.08 mole) of the trichloride was added t o a solution of 10 g. (0.18 mole) of potassium hydroxide in 40 cc. of ethanol. The temperature rose to 45' and potassium chloride began to precipitate out. The mixture was permitted to set overnight, the potassium chloride (6 g., 0.08 mole) was filtered off, and the filtrate was washed, dried and distilled. There was obtained 6.0 g. (0.04 mole) of product boiling a t 55" a t 40 mm. (138"
80
d 60 %
I
2 40
20 0
9.0 10.0 11.0 12.0 13.0 14.0 Wave length, microns. absorption spectrum of l,l-dichloro-3,3dimethyl-1-butene.
8.0 Fig. 1.-Infrared
8.0 9.0 10.0 11.0 12.0 13.0 14.0 Wave length, microns. Fig. 2.-Infrared absorption spectrum of l,l-dichloro-3methyl-1-butene. (4) L. Schmerling, THISJOUBNAL., 68, 1856 (1946).
FURFURYL AND THENYLALKYLAMINES FROM SCHIFF BASES
Feb., 1949
a t 760 mm.) ; n% 1.4530. The infrared absorption spectrums of this product was identical with that of I1 (Fig. 1). 1,1 -DichloroJ-methyl-1 -butene (111) .-The infrared spectrum of this compound was identical with that of the product obtained by the dehydrochlorination of 1,1,2trichloro-3-methylbutane, the condensation product of isopropyl chloride and cis-di~hloroethylene~ (Fig. 2). The dehydrochlorination of 17 g. (0.10 mole) of the trichloride by the procedure described above for the dehydrochlorination of 1,1,2-trichloro-3,3-dimethylbutaneyielded 6 g. (0.08 mole) of potassium chloride and 6.5 g. (0.05 mole) of product boiling a t 115-116" a t atmospheric pressure; n a o1.4460. ~ 1 , l -Dichloro-2-cyclohexylethylene(IV) .-Hydrolysis of 10 g. of this compound by heating with 100 g. of water at 275 O for four hours vielded 5 e . of an organic acid boiline a t 244-247" and melting a t 2 g 2 9 " . I< yielded an a$de The reported: properties of cyclomelting a t 166-167 hexaneacetiz acid are: b. p. 2 4 k 2 4 7 ; m. p. ranging from 27 to 32-33 ; amide, m. p. 168 , 171-172' (cor.).
.
( 5 ) The author is indebted to Dr. W. S. Gallaway, Physics Department, Universal Oil Products Company, for the infrared absorption analyses reported in this paper. For a description of the procedure used, see THISJ O U R N A L 69, 1124 (1947). (6) Beilstein, 4th ed., Vol. IX, p. 14.
703
Acknowledgment.-The author wishes to thank Mr. J. P,West for assistance in this work. Summary The condensation of t-butyl chloride with vinylidene chloride in the presence of ferric chloride yields a mixture of l,l,l-trichloro-3,3-dimethylbutane and l,l-dichloro-3,3-dimethyl-l-butene, the relative amounts of the two products depending chiefly on the reaction temperature. The aluminum chloride catalyzed condensation of the secondary chlorides, isopropyl chloride and cyclohexyl chloride, with vinylidene chloride yields as major products the unsaturated dichlorides, 1,ldichloro-3-methyl-1-butene and 1,l-dichloro-2cyclohexylethylene respectively. 1,1,l-Trichloroethane, formed by the hydrochlorination of vinylidene chloride is a by-product in both cases. RECEIVED JULY 22, 1948
RIVERSIDE,ILL.
[CONTRIBUTION FROM THE DEPARTMENT OF CHEMISTRY OF ST. VINCENT COLLEGE]
Furfuryl and Thenylalkylamines from Schiff Bases1B2 BY BERTINL. EMLING, J. E. BEATTYAND J. R. STEVENS
A number of secondary amines have been prepared3 by the action of organomagnesium halides on Schiff bases. However, since none of the furfurylideneamines or thenylideneamines have as yet been utilized in this type of reaction, i t was decided to investigate their behavior. Six isomeric alkylfurfurylamines have been prepared as represented by the equations
C4H30-CH=N-R'
f RMgBr
Amine Methyl Ethyl Propyl Butyl Amyl Butyl'
B. p.,
OC.
53 67 87-88 90 104-105 112-113
Mm. 16
18 21 13 10 13
Yield,
%
85 86 90 90 85 90
%*OD
1.5269 1.5170 1.5105 1.5057 1.5024 1.5459*
N Analyses, % d * b Calcd. Found 1.025 1 2 . 8 12.6 0.988 11.4 11.2 0.967 1 0 . 2 10.1 0.950 9.26 9.21 0.940 8.48 8.35 0.99ob 12.0 1t.Qc
Thenylideneamine. B*'D and d%. for CoHlsS: S, 19.2. Found: S, 19.1.
(hydrolysis) _____)
C4HaOCH(R)-NHR'
TABLE I
N-ALKYLPURPURYLIDENEAMINES
(1)
One thenylamine, C4H&-CH(CzHb)-NH(C4Hg), was also prepared from thenylidenebutylamine and ethylmagnesium bromide. The Schiff bases prepared and used in the syntheses are listed in Table I. The methyl- and ethylfurfurylideneamines were prepared by Schwabbauer4 who lists only their boiling points. The remaining Schiff bases are not described in the literature. Table I1 lists the furfurylamines, synthesized from the Schiff bases, and their a-naphthylurea derivatives. The ureas were prepared from the amines and anaphthyl isocyanate. (1) Presented before the Organic Division a t the 114th meeting of the American Chemical Society, Washington, D. C., Aug. 30Sept. 3, 1948. (2) The authors wish to acknowledge the assistance of John Heid, Harvey Patterson, Glenn Johnson, Ernest Goral, Thomas Solomon and Walter Hubis in some of the experimental work. (3) (a) Campbell, et ol., THISJOURNAL, 70, 3868 (1948); (b) Mo5ett and Hoehn, ibid., 69, 1792 (1947); (c) Gilman, Kirby and Kinney, ibid, 81, 2252 (1929). (4) Schwabhauer, Bcr., S I , 4 1 0 4 1 5 (1902).
e
Anal.
Calcd.
Gilman, Kirby and KinneySoreported a case of 1,4-addition to benzophenone ani1 under reaction conditions involving high temperature and a long period of heating. While we were of the opinion that 1,a-addition to the carbon-nitrogen structure took place under the mild conditions used in our reactions we desired to prove this. For this purpose one of the furfurylamines was synthesized from furan
-
NHpOH C~H~O-COCZH~ ___f CdHsO-C(NOH)CnHa
Na
CzHsOH
C4H30-C(H) (NHCaHo)(CHzCH3) (I)
The amine, I, was not isolated but reacted in ligroin with a-naphthyl isocyanate to give the corresponding urea, 1-butyl-1-(a-ethylfuryl)-3-( a-naphthy1)-urea.
