HENNION A N D BUTLER
VOL. 27
111. fl-Chloroamines and Aziridines’
Sterically Crowded Amines.
G. F. HEXXIOX AND PETER E. BUTLER^ Chemical Laboratories of the University of Notre Dame, A‘otre Dame, Ind. Received December 18, 1961 Tetra-substituted axiridines, R1R2d-CH(CH3)-k-R3, were prepared by cyclization of p-chloroamines, It11t2C(NHR3)-CHCl--CH3. The chloroamines of indicated structure mere obtained by treatment of the corresponding 8amino alcohols with thionyl chloride. Methods are described for the preparation of sterically crowded aziridines.
nature of the various products were studied in detail in the case of l-isopropyl-2,2,3-trimethylaziridine (XI) and related compounds correlated as shown. The fact that the amines A,D,E, and XVIII and their hydrochlorides were already known aided significantly in the assignment of the structures 11,XI, XVI, and XVII. Treatment of 3-isopropylamino-3-methyl-2-butano13 (preferably as the hydrochloride3 in chloroform) with thionyl chloride yielded a chloroamine
Mention was made in a previous paper3 that 1,2,2,3-tetra-substituted aziridines may be prepared from certain sterically crowded /?-amino alcohols via the intermediate 0-chloroamines. The synthesis involves the steps A-+B+C-.II+XI shown in Fig. 1. These transformations and the (1) Paper no. 78 on substituted acetylenes; previous paper, G. F. Hennion a n d Leonard Price, J. Org. Chem., 27, 1 3 7 (1962). ( 2 ) Eli Lilly Company Fellow, 1959-1961. Abstracted in part from the Ph.D. dissertation of P. E. B. (3) G . F. Hennion a n d P. E. Butler, J . Org. Chem., 26, 3341 (1961).
XH-CH( CHa)?
H2
1 I
Pd
NH-CH( CH3)2
2H2; Ni
/
NH-CH( CH3)2 ( CH3)2(!&C=CH
-
€120 -
H + ;Hg++
I
NH-CH( CHa),
1
(CHa)&-CO-CH3
NH-CH( LiAlHd __f
I
r
(CHa)&-CH(OH)-CHa
(B)
(A)
CH3)2
SOCll
CH(CHs12
C1
I A
PU”-CH(CH3)2
N
HC1
(CHa)?b-bH-CHa
t--
(CHa)zC-CH-CHa
AH3
I
NH-CH( CH3)2 BOB C-
c:
(CHa), -CHCl-CH,
(XVII)
H1; Ni
NH-CH( CHa)2
I
(CHa)&H-CH-CHa
(XVIII)
Fig. 1.-1-Isopropyl-2,2,3-trimethylaziridine and related compounds.
JUNE,
2089
STERICALLY CROWDED AMINES.I11
1962
TABLE I ~ C H L O R O A MHYDROCHLORIDES, IXE R'RZC( XHR3)-CHCl-CH3.HCl M 01. Formula
Yield,a Compd.
RL
RZ
%
R3
h1.P.b
--Carbon. %-Calcd. Found
-Hydrogen, yoCalcd. Found
Nitrogen, % Calcd. Found
9 . 2 1 9.01 C7HljClgS 45.17 45.42 51 185-166' CgH5CHaCHa9 . 5 7 9.74 C8H1gC12N 48.00 48.18 73 157-158 CH3i-CaH7CH,9.88 9.96 CgH21C12N 50.46 50.30 69 166-167 CH3t-C4H9CHZ9.57 9 . 4 3 48.00 48.33 C2HS35 15G-158 CsHlgC12N CHaCgH5Ir CHgC2H5i-C3H760 126-127 C9HglC12N 50.46 50.78 9.88 9.99 CloHzgC1,S 52.63 52.71 10.16 10.27 28 135-136 CHZCgHbt-C4H9IrI 52.63 52.41 10.16 9.85 i-CgHj48 147-148 CioH23ClgY C2H5C2H:VI1 9.65 9 . 4 0 CiiHzaC12N 55.00 54.80 i-CgH755 13Sd VI11 -CH,(CH?)3CHg9.91 9.94 56.69 57.07 t-C4Hg47 142-143 CnHgsC12N -CH?(CHZ)3CHzIX Softened a t 158'. Melting points are for analytical samples. a Yields are for once crystallized products. then melted over xide range.
I
I1 I11 IV
7.53 7.23 7.00 7.19 6.54 6.62 7.00 7.10 6.54 6.75 6.14 6.01 6.14 5.88 5.83 6.08 5.51 5.53 Softened,
TABLE I1 TETRASEBSTITUTED AZIRIDINES, R1R2d-CH( CH&-k-1i3 Yield,a Comid.
Rl
KZ
R3
%
B.P.* h l m .
X CHIC:H:iC?H:69 97-98 73 112 CHaCH,- i-CaH,SI CHs- t-C4H969 129 XI1 CHg73 139 C?Hb-- i-CaHjXI11 CHIXIV -CHZ(CH*)aCHgi-C:3Hj59 98 35 XV -CH2(CHg)&H2t-C4H9-- 56 107 35 a Yields correspond t o once or twice distilled material
TL~
