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Reactive Derivatives of Aliphatic N-SulfinylaminesЧAlkylation of N-Sulfinylalkylamines and Bis (tert-butyl)-sulfur Diimide.

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R ~ N S O+ R;[email protected]~
--":
N%O
B F t~ R ~ O
RZ'
(1)
RX
MY
NaOAc
NaOAc
KSCN
KSCN
KF
K Br
KN02
NaCN
Solvent
CHnCN
CH3CN
CH3CN
CH3CN
CHnCN
CH,CN
CH2C12
CHnCN
t [a]
[hl
Conversion
4.5 [c]
5.0
1 .5
2.0
25.0
5.0
30.0
10.0
100 [d]
61
12)
(3a), R' = R2 = CH,
(36), R' = CzHs, R2 = CH3
[%I P I
100
c1.
98 [el
30
39
32
88
Thus the immonium salt (3a) is obtained in 97% yield
by direct reaction of the amine without solvent at 15°C [m.p.
72-75°C; 'H-NMR (in CD3N02):6=4.02 (6H) s]. The ethyl
derivative can be prepared analogously [oil; 'H-NMR (in
CD3CN): 6=1.52 (3H) t, 3.82 (3H) S, 4.35 (2H) q, J=7Hz].
N,N'-Bis(tert-buty1)sulfur diimide ( 4 ) can also be monoalkylated by the same procedure:
[a] We have not optimized the reaction time. [h] Determined by GLC.
[c] After 1 h, conversion 81 %. [d] Without catalyst, conversion -10%.
[el The same results with and without catalyst.
If a solution of alkyl halide or methanesulfonate in acetonitrile or dichloromethane with an excess of a dried and ground
sodium or potassium salt (Table) and 1--3 % of Aliquat 336
(trade name for technical grade methyltrioctylammonium
chloride) then a nucleophilic substitution takes place. The
tabulated data evidence a strong catalytic effect of the quaternary ammonium compounds. The fact that they are somewhat
less effective catalysts than crown ethers is, in our opinion,
due to different structures of solubilized ion pairs (cation-anion
interactions).
In the case of specific examples suitable choice of catalyst
and optimization of the reaction conditions may greatly
improve the yields.
Received: September 8, 1977 [Z 848 IE]
German version: Angew. Chem. 90, 58 (1978)
The salts ( j a ) [m.p. 124°C (dec.); 'H-NMR (in CD3N02):
6=1.64 (9H) s, 1.73 (9H) s, 3.71 (3H) s] and ( 5 b ) [m.p.
108°C (dec.); 'H-NMR (in CD3N02): 6=1.37 (3H) t, 1.66
(9 H) s, 1.73 (9 H) s, 4.35 (2H) q, J = 7 Hz] were synthesized
in 91 and 92 % yield, respectively.
As electron-deficient N-sulfinyl compounds[21, the
immonium tetrafluoroborates (3) are very suitable for cycloaddition reactions. For example, ( 3 a ) reacts cleanly with
2,3-dimethylbutadiene in acetonitrile to form the adduct (6)
[m.p. 86-88°C; 'H-NMR (in CD3N02): 6=1.83 (6H) s
(br) (CH3C=), 3.16 and 3.27 (6H) s (CH3N),3.60--4.60 (4H)
m (CH2S and CH2N)].
CAS Registry numbers:
C6H&H,Cl, 25168-05-2; C 4 H 9 0 S 0 2 C H 3 , 1912-32-9; C4H9Br, 109-65-9;
NaOAc, 127-09-3; KSCN, 333-20-0; KF, 7789-23-3; KBr, 7758-02-3; K N 0 2 ,
7758-09-0; NaCN, 143-33-9; methyltrioctylammonium chloride, 5137-55-3
C. J. Pedersen, H. K. Frensdorff, Angew. Chem. 84, 16 (1972); Angew.
Chem. Int. Ed. Engl. 1 1 , 16 (1972).
G . W Gokel, H. D. Durst, Synthesis 1976, 168.
C. L. Liotta, H. P. Harris, J. Am. Chem. SOC.96, 2250 (1974).
a) C. M. Starks, J. Am. Chem. SOC. 93, 195 (1971); b) C . M. Sturks,
R. M. Owens, ibid. 95, 3613 (1973); c) cf. also E. V. Dehmlow, Angew.
Chem. 89, 521 (1977); Angew. Chem. Int. Ed. Engl. 16, 493 (1977).
Some patents claim synthesis of isocyanates from alkyl halides in a solidliquid system catalyzed by TAA chlorides, e.9. Y. Nadachi, M. Kogura,
Jpn. Pat. 7595289 (1975); Chem. Abstr. 84, 164852 (1976).
Reactive Derivatives of Aliphatic N-SulfinylaminesAlkylation of N-Sulfinylalkylamines and Bis(tert-butyl)sulfur Diimide
By Gunter Kresze and Michael RossertC']
N-Sulfinyldimethylimmonium hexachloroantimonate is a
known compound[']. We have now found that compounds
of this type are readily accessible by alkylation of aliphatic
N-sulfinylamines (I ) with trialkyloxonium tetrafluoroborates
(2):
[*] Prof. Dr. G . Kresze, Dipl.-Chem. M. Rossert
Organisch-chemisches Institut der Technischen Universitat Miinchen
Lichtenhergstrasse 4, D-8046 Garching (Germany)
Angew. Chem. Int. Ed. Engl. 17 ( 1 9 7 8 ) No. 1
Hydrolysis of (6) leads to the (I-buten-4-y1)ammonium
salt ( 7 ) , m.p. 90-92°C.
General procedure
N-Sulfinylalkylamine (13 mmol) is added to trialkyloxonium
tetrafluoroborate (10 mmol) at 15"C and the mixture is allowed
to react at this temperature for 10h. The crude product is
washed [(3a)] or extracted [(36)] with a large amount of
dichloromethane and dried in uacuo.
The preparation of ( 5 a ) and ( 5 b ) can be performed in
analogous manner except that dichloromethane is used as
solvent. The crude product can be recrystallized from dichloromethane/ether.
Received: October 13, 1977 [Z 868a IE]
German version: Angew. Chem. 90, 61 (1978)
CAS Registry numbers:
( I ) , 4291-05-8; (2a), 420-37-1; (2b), 368-39-8; (3a), 65149-75-9; (361,
65 149-77-1 ;(4),2056-74-8;(5a),65 185-55-9; (Sb), 65 149-79-3 ;( 6 ) , 65 167-93-3;
(7), 65149-81-7; 2,3 dimethylhutadiene, 513-81-5
[l] W Warthmann, A. Schmidt, 2. Anorg. Allg. Chem. 418, 61 (1975).
[2] Review: G. Kresze, W Wucherpfennig, Angew. Chem. 79, 109 (1967);
Angew. Chem. Int. Ed. Engl. 6, 149 (1967).
63
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sulfinylaminesчalkylation, sulfinylalkylamines, butyl, aliphatic, sulfur, tert, bis, diimide, reactive, derivatives
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