close

Вход

Забыли?

вход по аккаунту

?

Cyclic DithiohemiacetalsЧSynthesis and Properties.

код для вставкиСкачать
Cyclic DithiohemiacetalsSynthesis and Properties[**]
Table 1. Cyclic dithiohemiacetals (Zu)to (2g) and iso-(2g) [a].
41",; b.p. 135"C/15 tom; 'H-NMR (60 MHz. CDC13): 6= 1.802.45 (m, 4H). 2.38 (d. J=6.5 Hz, IH), 2.55-3.20 (m, 2H), 4.60 (sm. 1 H):
MS: M i 12W28). 87(100), 85(20), 59(17), 58(10), 53(15), 45(56).
( 2 b ) . Yield 5 6 % ; b.p. 65"CjO.I torr; 'H-NMR (60 MHz, CDCI,): 6= 1.45JAX+JBX=12
2.40(m,6H),2.ll (d,J=7Hz,IH),2.55-2.85(m,2H),4.00(ddd,
Hz, J m = 7 Hz, IH); MS: M' 134 (27). 101 (100). 85 (17), 67 (40). 59 (30). 55 (12).
47 (12). 45 (38).
(Zc): Yield 53%; b.p. 75TjO.Ol torr: 'H-NMR(100 MHz, CDC13):S = 1.4%
2.10 (m, 8H), 2.26 (d, J = 6 Hz. IH). 2.30-3.10 (m, ZH), 4.24 (sm, IH);
MS: M' 148 (21). 115 (loo), 87 (II), 81 (36). 73 (14), 61 (33), 60 (11). 59
(13), 55 (15). 47 (12). 45 (28).
fZd):Yield:38%; b.p. 125"C/0.2torr; 'H-NMR(60 MHz,CDCI,): 6 = 1 . 3 0 - ~
3.00 (m, 6H), 2.15 (d. J=9.5 Hz, IH), 3.12 (s, 3H), 3.20 (s, 3H), 3.95 (ddd,
J A X + J B X = I ~ . ~ Hz. J m = 9 . 5 HZ, IH!: MS: M + 194 (7), 163 (27), I62 (loo),
133 (38). 129 (961, 128 ( 9 3 %127 (24), 103 (27), 101 (60), 97 (48), 88 (12),
87 (11). 86 (lo), 85 (5% 75 (181, 74 (16). 73 (100). 59 (53), 58 (15) 57 (20),
55 (29). 45 (58).
(Ze): Yield 69%; m.p. 55-56°C (benzene/ether); 'H-NMR (100 MHz, C,D,):
b=1.55-1.85 (m, 3H), 197 (d, J = 9 . 3 Hz, IH), 2.11-2.57 (m. 2H). 2.83
(ddd, IH), 3.56 (sm, 4H), 3.92 (ddd, J A X + J B X = I Hz,
~ . ~JsH=9.3 Hz, IH):
MS: M t 192 (27). 159 (72), 132 ( 1 3 , 131 ( 2 9 , 130 (Q), 99 (loo), 87 (11).
86 (22). 72 (20). 59 ( I 1 ).
( 2 1 ) : Yield 41 'a: m.p. 80°C (ether); 'H-NMR (60 MHz, CCDI):6 = 1.052.40 (m. 6H). 2.04 (d, J = I O Hz. 1H). 2.60-3.20 (m. 2H). 3.50 (sm, 4H),
4.05 (ddd. J A X + J B X = I ~ . ~HZ, J , ~ = 1 0 Hz, IH); MS: M' 206 (33), 173
(78), 172 (3% 146 ( 4 3 %145 (50). 144 (16), 115 (60), 113 (loo), 100 (29), 85
(5% 86 (22!, 73 (301, 71 (lo), 59 (30), 58 (17), 55 (43), 45 (35).
(29): Yield 28%; b.p. 120°Cc/0.3torr: 'H-NMR (60MHz, CDC13):6= 1.292.90 (m, 6HJ, 2.26 (d, J = 9 Hz. IH), 3.36 (s, IHJ, 3.57 (tt, IH), 3.86 (ddd,
J A X + J B X = I ~ . ~Hz, J s ~ = 9Hz, IH); MS: M t 150 (25), 117 (loo), 99 (15),
97 (lo), 89 (251, 88 (101, 87 (lo), 75 (40), 73 ( 5 9 , 61 (IS), 60 (15), 59 (15).
58 (If), 57 (15), 45 (25); 1R (CCI4):3500, 3595 cm-'.
i.so-lZol' Yield 41''L. h n 12O"Cin.? torr: 'H-NMR 160 MHz. ('DCI,).
d=l.lU-3.iU(Ill,
bHJ, L . l a ( a . J = X HZ, I H ) , j . U U ( S , 1Hj. 4.15 (sm, I H ) ,
4.42 (sm, IH): MS: M i 150 (4) 117 (loo), 99 (lo), 89 (25). 75 (32). 73
(631, 61 (15). 59 (15), 58 (10). 45 (30); IR (CCL): 3500, 3595 cm-'.
(Za): Yield
By Hans-Joacltim Gais[*I
Whereas ring-chain tautomerism and the anomeric effect
in cyclic hemiacetals ( 1 ) have long been recognized as fundamental phenomena-e.9.
in carbohydrate chemistry[']nothing has yet been reported about the behavior of the
sulfur analogs of (1 ), the cyclic dithiohemiacetals (2)['].
We report here on the synthesis and properties of the cyclic
dithiohemiacetals ( 2 u ) to ( 2 s ) and is0-(2g). They are the
first representatives of this new class of compounds[31,for
whose synthesis the reaction sequence (3)-+(4)-+(5)+(2)
has proven the most advantageous.
[a] Yields w. r. t. ( 3 u ) t o (39); b.p. on bulb-tube distillation; mass spectra:
relative intensity in %.
(ej
I
n
I
In accordance with this finding, and in contrast to (I ),
the diastereomeric 2-mercapto-I-thia-4-cyclohexanols(29)
and iso-(2g) are configurationally stable"] and d o not undergo
mutual transformation, even in the presence of acids or bases.
Preliminary H-NMR investigations of the conformational
equilibrium in ( 2 a ) to ( 2 9 ) and iso-(2g) provide evidence
The cr-chlorosulfides ( 4 a ) to ( 4 g ) and iso-(4g), which are
of an anomeric effect comparable in magnitude to that found
readily accessible from the sulfides ( 3 a ) to ( 3 9 ) by reaction
in
cyclic dithioacetals[*I. Interestingly, however, ( 2 d ) to ( 2 9 )
with N-chlorosuccinimide (NCS) in carbon tetrachl~ride[~.~I,
exist
almost exclusively in the conformation with equatorial
are converted by thiourea into the stable isothiouronium salts
arrangement of the mercapto group.
( 5 a ) to ( 5 g ) and iso-(5g). From these the dithiohemiacetals
( 2 a ) to ( 2 9 ) and iso-(2g) can be obtained in satisfactory
Experimental:
yields (Table 1) as colorless, liquid or crystalline compounds
having a characteristic odor; they are stable over prolonged
( 2 e ) : N-Chlorosuccinimide (0.17 mol) is added with stirring
periods of time, both in substance and in solution, and only
to a solution of (3e) (0.16 mol) in carbon tetrachloride (400ml)
slightly sensitive to oxidation[61.
at 0°C. After 2 h at 0°C-a 'H-NMR spectrum of the reaction
The 'H-NMR spectra (Table I), providing proof of the
solution indicates the almost quantitative formation of ( 4 e )
cyclic structure of the dithiohemiacetals ( 2 ) , give no indication
[(60MHz, CCI4): 6=2.74-2.40 (m, 4H), 2.563.00 (m, 2H),
of a ring-chain tautomerism with the open-chain mercapto3.96 (s, 4H), 4.98 (dd, JAX
+ Jsx = 14 Hz, 1H)]-the reaction
thioaldehyde- ( 6 ) and mercaptovinylthiol-form ( 7).
mixture is filtered and treated at 0°C with a solution of
thiourea (0.17 mol) in anhydrous acetone (300ml). Filtration
[*] Dr. H.-J. Gais
and washing with acetone yields 34.1 g (79%) of crystalline
lnstitut fur Orgdnische Chemie der Technischen Hochschule
( 5 e ) , m.p. 115-116"C, which is dissolved in l00ml water
Peterseiistrasse 22, D-6100 Darmstadt (Germany)
and treated dropwise at 0°C with a solution of sodium hydrox[**I This work was supported by the Deutsche Forschungsgemeinschaft.
ide (0.36mol) in water (80ml). After 2 h at 0°C the solution
These investigations were carried out in part at the Department of
Chemistry at Harvard lrniversity (Prof. R. B. Woodward).
is acidified with ice-cold 2 N sulfuric acid, extracted with di-
'
196
Aiiqrw. C h m . Int. Ed. Enql. 16 (1977) No. 3
chloromethane, and the organic phase washed with saturated
N a H C 0 3 solution and evaporated to dryness. The residue
is dissolved in .a little dichloromethane and filtered with dichloromethane/n-hexane( 1: l)oversilicagel60(Merck).Evaporation to dryness and recrystallization of the residue from
benzene/ether affords 21 g (87%) of colorless crystals, m.p.
5 5-56 "C.
Received: December 9, 1976 [Z 628 IE]
German version: Angew. Chem. 89, 201 (1977)
CAS Registry numbers:
(Zu), 61477-08-5;(2h). 61477-09-6:(2c). 61477-10-9;( 2 d ) , 61477-11-0;
( 2 r ) . 61477-12-1;
( 2 f ) . 61477-13-2;(291, 61477-14-3:is0-(2g), 61477-15-4;
( 3 a ) , 110-01-0: ( 3 h ) . 1613-51-0;( j c ) , 4753-80-4:(3d), 61477-16-5;(3e),
42850-68-0:(3f), 61010-86-4;( 3 g ) , 29683-23-6:( 4 0 ) , 22342-03-6;( 4 b ) ,
22342-04-7: ( 4 c ) , 22342-10-5:( 4 d ) , 61477-17-6:( 4 e ) , 61477-18-7:( 4 f ) ,
61477-19-8;( 4 ~ ) 61477-20-1:
.
iso-(4q). 61477-21-2:(5~). 61477-22-3:( 5 b ) ,
61477-23-4;( 5 1 ) . 61477-24-5;( 5 d ) , 61477-25-6:(5c), 61477-26-7:(51).
61491-1L O : ( 5 9 ) . 61477-27-8:iso-fjg), 61477-28-9:N-chlorosucciniinide.
128-09-6:thiourea, 62-56-6
J . F. Sroildurr: Stereochemistry of Carbohydrates. Wiley-Interscience.
New York 1971.
Little is kiiown about the behavior of cyclic monothiohemiacetals. Cf.
T. Sheradsky in S Patai: The Chemistry of the Thiol Group. Wiley,
London 1974.Vol. 2,p. 685 and literature cited therein; M . C. Missakian,
R. Ketchum, .4. R. Murfin, J. Org. Chem. 39, 2010 (1974).
For the synthesis of acyclic dithiohemiacetals, cf. H. C . Peer, A . van
der Heijdeii. S. B. Tjan, T L. i w i Onlei?, Synth. Comniun. 1, 277 (1971)
and literature cited therein.
D. L. Tidren, R. H . Benriett, J . Heterocycl. Chem. 6, 115 (1969).
The acetate of ( 3 9 ) was used as starting material for the synthesis
of (29) and i s 0 4 2 g ) .
Correct elemental analyses were recorded for ( 2 a ) to ( 2 y ) and is0-(2g).
The diastereoisomeric (7-mercapto-1,5-dioxa-~-thiaspiro[5.5]undec-l0y1)methanols are also configurationally stable. K. Tarsutu. Keiso University. Hiyushi, Yokohama (Japan), private communication.
N. S. Zejiroc, I/. S . Blagoceshcheiiskii. I . V Kazimircliik, 0. P . Yakoilem,
J. Org. Chem. (USSR) 7, 599 (1971):M . Oki, 7: Sugawuru, H . Iwamura,
Bull. Chem. SOC.Jpn. 47, 2457 (1974).
Analysis of the vibrational spectra ought to further clarify
the problem. IR spectroscopy would be better suited for the
detection of O H groups and Raman spectroscopy for the
detection of SH groups[41.Great experimental difficulties are
met with in recording the IR spectra of superacids; added
to this the superacid itself contains O H groups.
We have investigated the Raman spectra of cu. 30 mol%
solutions of ( I ) and of dimethyl sulfide (2) in 100% magic
acid (HSO3F-SbF5, 1 : 1 ) (Raman spectrometer Coderg PHO
with low-temperature measuring cell, -40 to +2O"C, argonion laser 5145
The spectra of the protonated species
show new bands and/or band shifts compared to those of
the pure compounds ( I ) and (2) and those of the pure
superacid (Fig. 1). Their interpretation in the region of the
skeletal vibrations below 1500 cm-' is rendered difficult,
since the signals of the protonated species in this region are
superposed by bands of the pure superacid and of the complex
ions in solutions of this typec6]. For compounds with SH
groups the signal of the S-H stretching vibration appears
above 1500 cm-' at 2550 to 2600 cm-'.
I
,
.
,
.
l
.
3000
l
.
l
.
l
.
l
.
l
.
l
.
1
.
2000
1
.
1
.
1
.
1
1000
.
I
.
l
.
~
.
l
O
_. 1100
~1UlJ
2000
3000
I
1000
1100
I
Site of Protonation of Dimethyl Su1foxide.-Raman
Spectroscopic Data[**]
By Manjred Spiekermann and Bernhard Sc/irader[*'
To understand the mechanism of acid catalyzed reactions
of sulfoxides, both the position of the acid-base equilibrium
as well as the location of the proton in the first step of
the reaction must be known['].
Dimethyl sulfoxide ( I ) contains two potentially basic
centers in the S=O group. Consequently a protonation of the
oxygen atom ( I a ) or the sulfur atom ( I b ) would be possible:
Investigations into the actual location of the proton in
protonated ( 1 ) with the aid of NMR spectroscopy have
led to contradictory finding^'^.^].
["I
[**I
Prof. Dr. B. Schrader, Dip].-Chem. M. Spiekermann
Abteilung Theoretische Organische Chemie der Universitiit
Postfach 500500, D-4600 Dortmund 50 (Germany)
New address: Teilbereich Physikallsche und Theoretische Chemie der
Universitlt-Gesamthochschule
Universitatsstrasse 2, D-4300 Essen 1 (Germany)
This work was supported by the Fonds der Chemischeu Industrie.
We thank Prof. Modeiia, Padua, and Prof. Kresze, Munchen, for introducing us to the problem.
Aiigebv. Chein. Itit. Ed. Enyl. 16 ( 1 9 7 7 )
No. 3
I
100
dl
1
I
.
9..
I 1
. I .
I . I . I . I . I
0
Fig. 1. Raman spectra of a) magic acid (MA), H S 0 3 F (100%): b) (CH&S
( 2 ) : c) 30 mol.% (2) in M A : d ) (CH&S=O ( 1 ): e) 30 mol.% f 1 ) in
MA [I=amplification x 1 : I I =amplification ~0.21.
In the spectrum of the protonated sulfide (2) the band
is observed quite clearly at 2550 cm-' (Fig. Ic), whereas
in the spectrum of the protonated sulfoxide (1 ) this region
is free of bands (Fig. te). In our opinion this affords a sure
indication of the absence of SH groups in the protonated
dimethyl sulfoxide and thus proof of the structure (1 a ) .
Received: January 7, 1977 [Z 646 IE]
German version: Angew. Chem 89. 200 (1977)
197
Документ
Категория
Без категории
Просмотров
0
Размер файла
226 Кб
Теги
properties, cyclic, dithiohemiacetalsчsynthesis
1/--страниц
Пожаловаться на содержимое документа