the addition of gem-dinitroalkanes to unsaturated nitro compounds

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THE ADDITION OF gem-DINITROALKANES TO UNSATURATED NITRO COMPOUNDS I. S. Ivanova, Yu. V. Konnova, and S. S. Novikov N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences, USSR Translated from Izvestiya Akademii Nauk SSSR, Otdelenie Khimicheskikh Nauk, No. 11, pp. 2078-2079, November, 1962 Original article submitted June 13, 1962 There ha~,e been sufficiently detailed studies of the reaction of addition of the simplest nitroalkanes to nitro- alkenes ['1]. The reaction of 1,1-dinitroethane with 1-nitro-l-alkenes [2] and 2-nitro-l-propene [3] has also been studied. As to the addition reaction at the activated double bond of unsaturated nitro compounds of other classes, esters of a, /5 -unsaturated acids and nitroalcohols, here there are no data at all. In order to explain the reactivity of the double bond in acrylic esters of nitroalcohols we have undertaken the present work. As the first objects we have used 1,1-dinitropropane, 1,1-dinitrobutane, and g,t~,B-trinitroethyl esters of acrylic acid [4]. We have found that this reaction occurs at room temperature in a methanol medium in the presence of ca- talytic amounts of sodium methylate NO~ NO2 RCH -~- CH2 = CIICOOCH2C (N()~)3-* RCCIt2CH.2COOCHeC (N O2)a I I NO2 NO.,. Pt =: C:~Hs, CaHT- For comparison we studied addition of the same gem-dinitroalkanes to 1-nitro-l-alkenes (to 1-nitro-l-propene, 1-nitro-l-butene, 1-nitro-l-pentene) NO2 NO2 I I RCIt = CH NO~-}- C~H~CH --~ NO2CIIaCII -- CC2It5 I I I NO2 R NQ R - - C H a , C~tts, p C.~ttT~ We showed that these nitroalkenes form the corresponding addition products with greater yields than the esters of trinitroethyl alcohol and acrylic acid and so we can assume (though for final conclusions kinetic study will be needed) that the double bond in nitroalkenes is more reactive in reactions of nucleophilic addition than the double bond in esters of unsaturated acids and nitroalcohols. EXPERIMENTAL The addition reaction was carried out in methanol medium at room temperature in the presence of several drops of 1 N or 10% solution of sodium methylate. The resulting addition products were purified either by distilla- tion in a nitrogen atmosphere or by recrystallization from aqueous alcohol. Preparation of 2,2,2-trinitroethy ! ester of 7,7-dinitroc.aproic acid. From 2.7 g 1,1-dinitropropane and 5.2 g of 2,2,2-trinitroethyl ester of acrylic acid we obtained 2.6 g (35.1% of the theory) of a substance with m.p. 58-54* (after recrystallization from aqueous alcohol, 2:1). Found: C 25.88; 25.96; H 3.18; 3.21; N 19.25; 19.19~]o. CsHllOIzNs. Calculated: C 26.09.; H 8.03; N 18.96%. Preparation of 2,2,2-trinitroethyl ester of 7,7-dinitroheptoic acid. From 1.9 g of 1,1-dinitrobutane and 8.8 g of 2,2,2-trinitroethyl ester of acrylic acid we obtained 0.85 g (17.3%of the theory) of a substance with m.p. 69- 70~ (after recrystallization from aqueous ethanol, 2: 1). Found: C 28.96; 28.51~; H 3.90; 3.74~ CgHI~OIzN 5. Calculated: C 28.47; H 8.42%. 1985

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Page 1: The addition of gem-dinitroalkanes to unsaturated nitro compounds

THE A D D I T I O N OF g e m - D I N I T R O A L K A N E S TO UNSATURATED

N I T R O C O M P O U N D S

I . S. I v a n o v a , Y u . V. K o n n o v a , a n d S. S. N o v i k o v

N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences, USSR Translated from Izvestiya Akademii Nauk SSSR, Otdelenie Khimicheskikh Nauk, No. 11, pp. 2078-2079, November, 1962 Original article submitted June 13, 1962

There ha~,e been sufficiently detailed studies of the reaction of addition of the simplest nitroalkanes to nitro- alkenes ['1]. The reaction of 1,1-dinitroethane with 1-n i t ro- l -a lkenes [2] and 2-n i t ro- l -propene [3] has also been studied. As to the addition reaction at the activated double bond of unsaturated nitro compounds of other classes, esters of a , /5 -unsaturated acids and nitroalcohols, here there are no data at all.

In order to explain the reactivity of the double bond in acryl ic esters of nitroalcohols we have undertaken the present work. As the first objects we have used 1,1-dinitropropane, 1,1-dinitrobutane, and g,t~,B-trinitroethyl esters of acryl ic acid [4].

We have found that this reaction occurs at room temperature in a methanol medium in the presence of ca - talyt ic amounts of sodium methylate

NO~ NO2

RCH -~- CH2 = CIICOOCH2C (N()~)3-* RCCIt2CH.2COOCHeC (N O2)a I I

NO2 NO.,. Pt =: C:~Hs, CaHT-

For comparison we studied addition of the same gem-dinitroalkanes to 1-n i t ro- l -a lkenes (to 1-ni t ro- l -propene, 1 -n i t ro - l -bu tene , 1 -n i t ro - l -pen tene)

NO2 NO2 I I

RCIt = CH NO~-}- C~H~CH --~ NO2CIIaCII - - CC2It5 I I I

NO2 R N Q

R - - C H a , C~tts, p C.~ttT~

We showed that these nitroalkenes form the corresponding addition products with greater yields than the esters of trinitroethyl alcohol and acrylic acid and so we can assume (though for final conclusions kinetic study will be needed) that the double bond in nitroalkenes is more reactive in reactions of nucleophilic addition than the double bond in esters of unsaturated acids and nitroalcohols.

E X P E R I M E N T A L The addition reaction was carried out in methanol medium at room temperature in the presence of several

drops of 1 N or 10% solution of sodium methylate . The resulting addition products were purified either by distilla- tion in a nitrogen atmosphere or by recrystallization from aqueous alcohol.

Preparation of 2,2,2-trinitroethy ! ester of 7,7-dinitroc.aproic acid. From 2.7 g 1,1-dinitropropane and 5.2 g of 2,2,2-trinitroethyl ester of acryl ic acid we obtained 2.6 g (35.1% of the theory) of a substance with m.p. 58-54* (after recrystall ization from aqueous alcohol, 2 :1) . Found: C 25.88; 25.96; H 3.18; 3.21; N 19.25; 19.19~]o. CsHllOIzNs. Calculated: C 26.09.; H 8.03; N 18.96%.

Preparation of 2,2,2-trinitroethyl ester of 7 ,7-d in i t rohepto ic acid. From 1.9 g of 1,1-dinitrobutane and 8.8 g of 2,2,2-trinitroethyl ester of acrylic acid we obtained 0.85 g (17.3%of the theory) of a substance with m.p. 69- 70 ~ (after recrystall ization from aqueous ethanol, 2: 1). Found: C 28.96; 28.51~; H 3.90; 3.74~ CgHI~OIzN 5. Calculated: C 28.47; H 8.42%.

1985

Page 2: The addition of gem-dinitroalkanes to unsaturated nitro compounds

Preparation of 1 ,3 ,3 - t r in i t ro -2-methylpen tane . From 1.9 g of 1 ,1-dini t ropropane and 1.0 g of 1-ni tropropene we obtained 1.25 g (49.2% of the theory)of a substance in the form of a colorless oi l with b.p. 109-110.5" (1 ram) and nD 2~ 1.4727. Found: N 18.80; 18.68%. C6HllO~,N s. Calcula ted: N 19.00%.

Preparation of 1 ,3 ,3- t r in i t ro-2-e thy lpentane . From 5.7 g of 1,1-dini t ropropane and 4.95 g of 1 - n i t r o - l - b u t - ene we obtained 7.5 g (75.0% of the theory) of a substance in the form of a colorless oil with b.p. 130-130.2" (2

ram) and nD z~ 1.4764. Found: C 35.79; 35.59; H 5.97; 5.77~ CTHtaO~N S. Calcula ted: C 35.'/4; H 5.57%.

Preparat ion of 1 ,3 ,3- t r in i t ro=2-n-propylpentane From 1.8 g of 1,1-dini tropropane and 1.95 g of 1 -n i t ro -1 - pentene we obtained 2.70 g (81.1% of the theory) of a substance in the form of a l ight colored oi l with b.p. 122- 123 ~ (1 mm) and nD 2~ 1.4750. Found: N 16.59; 16.41%. CsHIsO6N s. Calcula ted: N 16.86%.

S U M M A R Y 1. We have shown for the first t ime the possibil i ty of addit ion of ni troalkanes to acry l ic esters of n i t roa l -

cohols in the case of 1 ,1-dini t ropropane, 1 ,1-dini t robutane, and 2,2 ,2- t r ini t roethyl ester of acry l ic acid.

2. We have obtained the previously unknown trinitroalkanes by addit ion of 1,1-dini t ropropane to 1 -n i t ro -1 - alkenes.

1.

2. 3.

4.

L I T E R A T U R E C I T E D S. S. Novikov, I. S. Korsakova, and K. K. Babievskii, Uspekhi Khimi i 26, 1109 (1957). S. S. Novikov, I. S. Korsakova, and K. K. Babievskii, Izv. AN SSSR, Otd. khim. n. 1959, 1480. H. Schechter and L. Zeldin, J. Amer. Chem. Soc. 7._3_3, 1276 (1951). H. Feuer, H. B. Hass, and R. D. Lowery, J. Organ. Chem. 25, 2070 (1960).

S T U D I E S BY T H E EPR M E T H O D OF R A D I C A L S F O R M E D

IN THE R E A C T I O N OF H Y D R O G E N A T O M S W I T H B E N Z E N E

L. I . A v r a m e n k o , N. Y a . K u b e n , R. V . K o l e s n i k o v a , V . A . T o l k a c h e v , a n d I . I . C h k h e i d z e

Insti tute of Chemica l Physics, Academy of Sciences, USSR Translated from Izvest iya Akademi i Nauk SSSR, Otdelenie Khimicheskikh Nauk, No. 11, pp. 2079-2081, November, 1962 Original a r t ic le submit ted June 15, 1962

For a study of the radicals formed in low temperature radiolysis there has recent ly been wide use of the method of e lec t ron paramagnet ic resonance (EPR). However, interpretat ion of the spectra which are found is often diff icult . This is connected with the possibi l i ty of simultaneous appearance of several radicals in the i r radia ted substance, and also with the poorer resolution of the spectra at low temperature. In this connect ion it is of inter- est to ana lyze the EPR spectra of individual radicals which can be obtained, for example , in gaseous reactions of atoms with s imple molecules . In the present work we have studied the free radicals formed in the e lementa ry re- act ion of a tomic hydrogen with a molecule of benzene. This react ion obviously plays an important part in the

mechanism of radiolysis of al l s imple aromat ic compounds.

E X P E R I M E N T A L The experiments were carried out on the apparatus described previously in the work of Avramenko and co -

workers [1, 2]. The hydrogen atoms were obtained from molecular hydrogen in a silent discharge (voltage 6000 V,

current strength 150 mA, pressure 20 m m Hg) and through a nozzle. At a distance of 10 cm from the nozzle the vapors of benzene were introduced into the stream. Near the point of introducing the benzene the react ion vessel entered a narrow glass tube which passed through a cyl inder f i l led with l iquid nitrogen; on the walls of this tube the benzene and the react ion products were frozen out as they came from the gas phase mixing of benzene and hy-

1986