CONCLUSIONS

The reaction of polyfluoroalkyl fluosulfates with either SbFs or tertiary amines leads to elimination of S02F2 and the formation of fluorocarboxylic acid fluorides. The reaction of 1,2-bis(fluosulfonyloxy)hexafluoropropane with SbFs gives pentafluoroethyl fluosulfate.

LITERATURE CITED

i. I. L. Knunyants, G. A. Sokol'skii, and M. A. Belaventsev, Izv. Akad. Nauk SSSR, Ser. Khim., 1966, 1017.

2. R. W. Alder, Chem. Ind., 20, 983 (1973). 3. H. H. Gibbs, W. L. Edens, and R. N. Griffin, J. Org. Chem., 26, 4140 (1961). 4. M. Hauptschein and M. Braid, J. Am. Chem. Soc., 83, 2500 (1961). 5. M. Hauptschein and M. Braid, J. Am. Chem. Soc., 83, 2505 (1961). 6. A. V. Fokin, Yu. N. Studnev, L. D. Kuznetsova, and V. L. Rud, Izv. Akad. Nauk SSSR,

Ser. Khim., 1974, 471. 7. M. Lustig and J. K. Ruff, Inorg. Chem., 3, 287 (1964). 8. J. J. Delfino and J. M. Shreeve, Inorg. Chem., 5, 308 (1966). 9. M. Lustig and J. K. Ruff, Inorg. Chem., 4, 1441 (1965).

i0. B. H. Gorth, U. S. Patent 3,555,100 (1971); C. A., 74, 87335 (1971). ii. A. M. Platoshkin, Yu. A. Cheburkov, and I. L. Knunyants, Izv. Akad. Nauk SSSR, Ser.

Khim., 1969, 112. 12. I. P. Kolenko, T. I. Filyakova, A. Ya. Zapevalov, E. P. Mochalina, L. S. German,

and V. R. Polishchuk, Izv. Akad. Nauk SSSR, Ser. Khim., 1979, 667. 13. J. C. Reid, J. Am. Chem. Soc., 69, 2069 (1947).

8-AMINOVINYL KETONES WITH TWO FLUOROALKYL SUBSTITUENTS

K. I. Pashkevich and A. Ya. Aizikovich UDC 542.91:547.447'161

The presence in 8-aminovinyl ketones (AVK) of an amino group on a C atom, attached to a fluoroalkyl substituent, leads to the appearance of a barrier of rotation around the C--N bond (55-59 kJ/mole), which is not observed for the isomeric AVK with a fluoroalkyl sub- stituent on the carbonyl group [i].

In order to study the effect of fluoroalkyl substituents on the value of the rotation barrier and the strength of the intramolecular hydrogen bond (IMHB) we synthesized a number A~<, (I)-(IV), with two fluoroalkyl substituents and studied the IR spectra and the tem- perature dependence of the PMR spectra. AVK (I)-(IV) cannot be obtained from the symmetrical polyfluorinated $-diketones and NH3 [2], and, consequently, a method was developed for the synthesis of these compounds via the reaction of NH3 with fluorine-containing B-chlorovinyl ketones.

nF~ p,~ ~F l~F RF SOCI~ ~ " ~ "~H__ ~ O\ ...O DMF CL O

H t/F=CF3 (I); H(CF2)~. (II); C3F 7 (III); H(CF~)~ (IV).

R F

<V Ntt~ 0 (I)--(~V)

The starting ~-chlorovinyl ketones were obtained by reacting symmetrical polyfluori- nated B-diketones with SOC12 in the presence of DMF as the catalyst [3]. The structure of AVK (I)-(IV) was proved by elemental analysis and the IR and PMR spectral data (Table i).

The IR spectra of (I)-(IV) in CCI~ solution have the bands of ~ C=O at 1650-1680 cm -l and ~ N--N at 3280-3300 and 3495-3502 cm -I. The substantial broadening of the band at 3280- 3300 cm -I, and also its independence of the concentration, both indicate that it belongs to the vibrations of the proton taking part in the IMHB. A decrease in the difference of the

Institute of Chemistry of the Ural Scientific Center, Academy of Sciences of the USSR, Sverdlovsk. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1908-1909, August, 1982. Original article submitted December 22, 1981.

1698 0568-5230/82/3108-1698507.50 �9 1983 Plenum Publishing Corporation

TABLE i. Fluorine-Containing ~-Aminovinyl Ketones

C o r n -

pound

(i)

(II)

(iii)

(Iv)

C o m -

pound

(i) (u)

(iii) (iv)

Yield,% rap, ~ H g ) - bp, ~ (p, mm

I c

42 34 subl.

61 42-43

54 64-66 (8)

65 91-92(2)

28,73

30,94

26.68

28,83

Found/talc., %

t,93 6.51 ~/-7~ 6.7-G-4 1,50 6s

1,01 3.61

I,CO 2,97

Empirical formula

CaHaF6NO

C7HsFsNO

CgHsFI,NO

CIIH~F~NO

Yield, I mP,o ~ bp, C % i (p, mmHgl vC=O

I

Infrar__ ed spectr______um, c_m-~ PMR spectrum, ppm

IlvtHB .~, ]

42 I 34subl, 61 [ 42--43 54 64--66(8) 65 91--92(2)

i680 1650 1670 1665

t628 330,0 3500 1625 3285 3500 1620 3280 3495 '1620 3280 3502

6.t 5185 5,8 5,8

IMHB 5CH 6NII

9.9 6,2 9,7 5,8 9,7 6,1 9,8 6,0

Nil frequencies (Av ~ 200-210 cm -I) in (1)-(IV) when compared with AVK that have only one fluoroalkyl substituent on the C atom attached to the amino group (Av ~ 230-280 cm -I) can be explained by a weakening of the IMHB in (1)-(IV).

In the PMR spectra of (1)-(IV) at ~20~ are observed one unsplit signal of a methine proton and two signals of nonequivalent NH2 protons at ~6 and ~i0 ppm (the latter belongs to the proton that takes part in the I~HB). A merging of the Nil signals occurs at 70-80~ evidently due to acceleration of the rotation around the C--N bond. From this temperature dependence as an approximation of slow exchange [4] were found the values AG~ = 62.8-63.2 kJ/mole. The presence of a quadrupoie moment on the N atom leads to a broadening of the PMR signals and correspondingly to an increase in the error of determining AG~ up to 10%. An increase in AG e for (I)-(IV) when compared with the AVK with one fluoroalkyl substituent (55-59 kJ/mole [i]) is probably related to an increase in the degree of conjugation of the unshared electron pair of N with the ~ system of the molecule, which leads to a greater stability of the cis-planar form.

EXPERIMENTAL

The PMR spectra were recorded on a Tesla BS-487 spectrometer in perfluorotoluene solu- tion in the range 20-120 ~ and using HMDS as the internal standard. The IR spectra were taken on a UR-20 spectrophotometer for 0.2% CCI~ solutions.

General Method for Preparation of AVK (1)-(IV). Into a benzene solution of i0 mmo!es of the B-chlorovinyl ketone (used immediately after preparation [3]) was passed NH3 from a cylinder, the obtained precipitate Was filtered, the filtrate was evaporated, and the AVK was recrystallized from hexane. The yields and constants of products (1)-(IV) are given in Table i~

CONCLUSIONS

i. A method was developed for the synthesis of B-aminovinyl ketones with fluoroalkyl substituents in the 2 and 4 positions of the chelate ring.

2. The barrier of internal rotation around the C--N bond in these compounds is 62.8- 63.2 kJ/mole.

i.

LITERATURE CITED

A. Ya. Aizikovich, K. I. Pashkevich, V. V. Gorshkov, M. N. Rudaya, and I. Ya. Postov- skii, Zh. Obshch. Khim., 50, 1866 (1980).

1699

~

3. 4.

S. C. Chottoray, A. G. Cupca, and R. E. Sievers, J. Inorg. Nucl. Chem., 28, 1937 (1966). R. Bauer, H.-P. Mfiller, and R. E. Sievers, Anal. Chem., 43, 2012 (1971). H. Kessler, Angew. Chem., 82, 237 (1970).

REACTION OF TETRAAMINOPYRIMIDINE WITH I-ARYLSULFONYL-4-METHYL-

IMIDAZOLIN-2-ONES

S. I. Zav'yalov and A. G. Zavozin UDC 542.91:547.85

Previously [i] it was established that in aqueous medium, in the presence of piperidine, tetraaminopyrimidine (I) reacts with the l-(benzenesulfonyl)-, l-tosyl-, and l-(4'-chloro- benzenesulfonyl)-4-methylimidazolin-2-ones (IIa-c) to give mixtures of the 6- and 7-methyl- 2,4-diaminopteridines (Ilia, b):

NH 2 0 NH 2 NH 2

N Rso2 NY Y ~" ~ N "% , 6 - & + +

2 H2 CH3 H2N H2N CH a

i0 (H~-i/ (UIa) (mh)

(IIa-i): R -- C~Hs(a), C6H~CHa-4'(b), CaIt,C1-4'(c), C~H,OCH~-4'(d), CsH,F-4'(e), C6HaCla-2', 5' (f), C6HaBr~-2',5' (g), C~H~Br-4' (D, C6H,NO~-4' (i).

In the present paper, in order to study the effect of the character of the substituents in the aromatic ring on the structural direction of this reaction, we condensed (I) with other l-(arylsulfonyl)-4-methylimidazolin-2-ones (lid-i) (Tables 1 and 2).

As can be seen from Table 2, in their effect on the relative yield of the 7-methyl iso- mer (IIIb), substituents in the p-position of the aromatic ring of (IIa-i) fall into the following order: C1 < CHaO < F < CHa < Br < H < NOa. An examination of this series permits concluding that an electron-donor character of the substituent favors the formation of the 6-methyl isomer (IIIa), while an electron-acceptor character favors the formation of the 7-methyl isomer (IIIb). The observed rule can be explained if we start with the previously [i] expressed concepts regarding the mechanism for the reaction of (I) with (IIa-c), which consists in the prior hydrolytic cleavage of (IIa-c) to the N-arylsulfonylaminoacetone (IV) and the subsequent cyclocondensation of (IV) with (I). In the next step of the process ketone (IV) reacts with (I) to give an equilibrium mixture of two imines (Va, b), in which imine (Va) predominates due to the higher nucleophilicity of the amino group at C s.

The cyclization of imines (Va, b), with cleavage of the arylsulfamido moiety, and sub- sequent dehydrogenation of the intermediate dihydropteridines (Via, b) by atmospheric oxygen, lead to the (Ilia, b) mixtures:

CHa NH2 IN H., / NH.., NH 2 NHSO2~

CH,, mo mo

H 2N N NH~ NHSO~R H2N N NH~ (Vb) XNCHa (Va) (I)

~ --H, NSO,R i --H,NS0,R

H N CH3 N

/ '~ (I l l a) (III b) N CHa H

(VI a) (VIb)

N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1910-1913, August, 1982. Original article submitted December 22, 1981.

1700 0568-5230/82/3108-1700507.50 ~9 1983 Plenum Publishing Corporation