Method of producing 1-azido-2-butyl-1,2-dihydro(c60-ih)[5,6]fullerene

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry, specifically to a method of producing 1-azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1) , which can be used as a complexing agent, sorbent and biologically active compound, as well as in production of novel materials with given properties. The method includes reacting fullerene C60 with tributyltin azide (n-Bu3SnN3) in the presence of a stoichiometric amount of Cu(OTf)2. The molar ratio C60:n-Bu3SnN3:Cu(OTf)2 is equal to 1:(1-5):(0.5-2). The reaction is carried out in a solution of dry chlorobenzene at 100°C in an argon atmosphere. The disclosed method enables to obtain 1-azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene (1) with output of up to 30%.

EFFECT: improved method.

1 tbl, 5 ex

 

The present invention relates to the field of organic synthesis, namely, to method of obtaining 1-azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1):

Derivatives of fullerenes with different functional groups can be used as donor-acceptor systems that mimic photosynthesis, which converts sunlight into electrical energy, generating reactive oxygen species, exciting radicals (antioxidants), showing semi - and superconducting properties, as well as ferromagnetism (Romanova I. P. "Electron-deficient mono - and bis-cycloadduct of fullerene C60. Synthesis, structure and properties", Thesis for the degree of doctor of science. Kazan, 2008 [1]).

The known method (General Jiang, Zuo Xiao, Gaihong Zhang, Liangbing Gan, Dian Wang, Wenxiong Zhang. Tetrahedron Lett., 2010, 51, 415 [2]) receiving stable at room temperature in the solid state fullerenelike (2) with a yield of 83% response C60(O2)(OOtBu)4(3) azidotimedinom in the presence of a Lewis acid chloride in dry the methylene chloride without access to daylight for 5 minutes at room temperature.

The known method does not allow to obtain 1-azido-2-butyl-1,2-dihydro (C60-Ih)[5,6]fullerene of formula (1).

Known with�persons (T. Tada, Y. Ishida, K. Saigo. Org. Lett., 2005, 26, 5897 [3]) obtain azidocarbonyl (4) with the release of ~84%, interaction chloroacetanilide (5) with a threefold excess acidoterrestris at room temperature for 30 minutes in bramasole.

The known method does not allow to obtain 1-azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1).

Thus, in the literature there are no data concerning the synthesis of 1-azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene (1).

A new method of obtaining 1-azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene (1).

The method consists in the interaction of fullerene C60(6) with tributylammonium (n-Bu3SnN3) in the presence of a stoichiometric amount of Cu(OTf)2taken in a molar ratio of C60:n-Bu3SnN3:Cu(OTf)2=1:(1-5):(0.5-2), preferably 1:2:1, in a solution of dry chlorobenzene at 100°C in argon for 1 h. Receive 1 azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene (1) with a yield of ~30%. The reaction proceeds according to the scheme:

n-Bu3SnN3Taking with excess relative to the fullerene C60with the aim of increasing the yield of the target product (1). Reducing the number tributylamine relative to C60netsales�brasno, as reduces output (1).

1 Azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene (1) is formed only with the participation of fullerene[60], tributylamine n-Bu3SnN3and Cu(OTf)2.

The reaction should be carried out at 100°C. conducting the reaction at room temperature due to the low yield of the resulting 1-azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene (1).

Significant differences of the proposed method

The proposed method is based on using as initial reagent tributylamine. The proposed method in contrast to the known allows to selectively receive 1 azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene (1), the synthesis of which is described in the literature.

The method is illustrated by examples.

In a glass dwparam the reactor was dissolved 20 mg (0.0277 mmol) C60in 4 ml of dry chlorobenzene was added with vigorous stirring a solution of (0,0554 mmol) Bu3SnN3in 1 ml of chlorobenzene and 10 mg (0.0277 mmol) of Cu(OTf)2. The reaction mass was heated to 100°C with stirring for 1 h. All experiments were performed in a stream of dry argon. After time the reaction mass is decomposed with 5% aqueous HCl, separated and the organic layer was passed through a small layer of silica gel. The reaction product 1 and fullerene C60shared with poliprep�exploring HPLC, eluent-toluene. The result was 1 azido-2-butyl-1,2-dihydro(C60-Ih)[5,6] fullerene (1) with a yield of 30% in the form of a brown powder.

Spectral characteristics (1)
The NMR spectrum13C (CDCl3:CS21:5, 100.62 MHz): 155.94, 149.27, 148.43, 147.86, 146.78, 146.54, 146.39, 146.36, 145.75, 145.60, 145.41, 145.38, 145.36, 144.97, 144.68, 144.43, 143.19, 142.88, 142.75, 142.44, 142.40, 142.34, 142.02, 141.56, 141.48, 140.12, 139.72, 136.92, 134.78, 80.16, 65.72, 41.75, 33.04, 24.40, 14.82. The NMR spectrum1H (CDCl3:CS21:5, 400.13 MHz): 3.56 (t, 2H, CH2, J=7.6 Hz), 2.51 (m, CH2), 1.88 (m, CH2), 1.29 (t, 3H, CH3, J=7.6 Hz). IR spectrum (KBr), v/cm-1: 527, 553, 574, 747, 1035, 1227, 2090, 2854, 2866, 2924, 2953. UV spectrum (CHCl3), λmax/nm: 257, 319, 430. The mass spectrum (MALDI TOF) found: m/z 777.067 [M-N3]-; C64H9; calculated: M=819.776 m/z C64H3H9.

Other examples of the method are shown in table.1

Table 1
№ p/pThe molar ratio of C60:n-Bu3SnN3:Cu(OTf)2mmolReaction time, hoursThe yield of the target product (1), %
11:1:1110
21:5:117
31:2:1130
41:2:0.5112
51:2:2125

Reactions were carried out at 100°C in dry chlorobenzene in an argon atmosphere, in the presence of a stoichiometric amount of Cu(OTf)2.

A method of producing 1-azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1)

characterized in that the fullerene C60interacts with tributylammonium (n-Bu3SnN3) in the presence of a stoichiometric amount of Cu(OTf)2taken in a molar ratio of C60:n-Bu3SnN3:Cu(OTf)2=1:(1-5):(0.5-2), in a solution of dry chlorobenzene at 100°C in an argon atmosphere.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry and specifically to a method of producing 1-bromo-2-azido-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1), which can be used as a complexing agent, a sorbent and a biologically active compound, as well as in production of novel materials with given properties. The method includes reacting fullerene C60 with bromine azide (BrN3), generated in situ from N-bromosuccinimide (NBS) and trimethylsilyl azide (TMSN3) in the presence of triflates of lanthanides and copper M(OTf)n (M=La, Sm, Yb, Cu; n=2, 3), with molar ratio C60:NBS:TMSN3:M(OTf)n=0.042:(0.042-0.063):0.754:0.042. The reaction is carried out at room temperature (about 20°C) in dry chlorobenzene for 1-4 hours under a current of dry argon without access to daylight.

EFFECT: disclosed method enables to obtain 1-bromo-2-azido-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1) with output of up to 30%.

1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of organic chemistry, in particular to method of obtaining 1-azido-2-ethyl-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1) , which can be applied as donor-acceptor system, imitating photosynthesis, which transform sunlight into electric energy, generating active forms of oxygen, capturing radials (antioxidants), as well as demonstrating semi- and superconductive properties. According to claimed method fullerene C60 interacts with diethylaluminiumazide (Et2AlN3), taken in molar ratio C60:Et2AlN3=1:(40-60), in solution of dry toluene at -20°C in atmosphere of argon with the following heating to 40°C for 2-4 h.

EFFECT: method makes it possible to obtain novel 1-azido-2-ethyl-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1) with output to 22%.

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FIELD: chemistry.

SUBSTANCE: invention relates to a novel method of obtaining alkyl (3R,4R,5S)-5-azido-3-(1-ethylpropoxy)-4-(mono or difluoro acetylamino)-cyclohex-1-enecarboxylates of general formula 1 and to a method of their application as half-products in synthesis of a nueramidase inhibitor of formula 18 In the said formulas R1=H,F; R2=C1-C3-alkyl. The method of obtaining general formula 1 compounds consists of interaction of alkyl(3R,4R,5S)-5-azido-4-amino-3-(1-ethylpropoxy)-cyclohex-1-enecarboxylate with fluoro- or difluoroactic acid in tetrahydrofuran at room temperature in the presence of hydrochloride of N1-((ethylamino)methylene)-N3, N3-dimethylpropane-1,3-diamine, 1H-benzo[d][1,2,3]triazol-1-ol and N-ethyl-N-isopropylpropane-2-amine. A compound 18 is obtained by reduction of the compound of general formula 1 with triphenylphosphine in aqueous tetrahydrofuran with the following interaction of the obtained compound with di-Boc-thiourea, hydrolysis of the obtained compound with lithium hydroxide in water dioxane and release of Boc-protection from the obtained acid with 30% solution of trifluoroacetic acid in methylene chloride.

EFFECT: obtaining intermediate products of general formula with application in the claimed method of the said reagents and conditions of reaction makes it possible to carry out the process more purposefully, reduce the quantity of side products and in that way simplify the process of obtaining and separation of the compounds.

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FIELD: chemistry.

SUBSTANCE: invention relates to organic synthesis and specifically to a method of producing functionally substituted fullerenes which can be used as donor-acceptor systems. The method of producing 1-iodo-2-azido(C60-Ih)[5,6]fullerene involves reaction of fullerene C60 with iodine azide, taken in molar ratio C60:IN3=1:(10-30), at room temperature (20°C) in chlorobenzene for 2-4 hours under a current of dry argon without access to daylight.

EFFECT: invention provides selective production of 1-iodo-2-azido(C60-Ih)[5,6]fullerene.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to organic synthesis and specifically to a method of producing functionally substituted fullerenes which can be used as donor-acceptor systems. The method of producing 1-iodo-2-azido(C60-Ih)[5,6]fullerene involves reaction of fullerene C60 with iodine azide, taken in molar ratio C60:IN3=1:(10-30), at room temperature (20°C) in chlorobenzene for 2-4 hours under a current of dry argon without access to daylight.

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FIELD: chemistry.

SUBSTANCE: invention relates to a novel method of obtaining alkyl (3R,4R,5S)-5-azido-3-(1-ethylpropoxy)-4-(mono or difluoro acetylamino)-cyclohex-1-enecarboxylates of general formula 1 and to a method of their application as half-products in synthesis of a nueramidase inhibitor of formula 18 In the said formulas R1=H,F; R2=C1-C3-alkyl. The method of obtaining general formula 1 compounds consists of interaction of alkyl(3R,4R,5S)-5-azido-4-amino-3-(1-ethylpropoxy)-cyclohex-1-enecarboxylate with fluoro- or difluoroactic acid in tetrahydrofuran at room temperature in the presence of hydrochloride of N1-((ethylamino)methylene)-N3, N3-dimethylpropane-1,3-diamine, 1H-benzo[d][1,2,3]triazol-1-ol and N-ethyl-N-isopropylpropane-2-amine. A compound 18 is obtained by reduction of the compound of general formula 1 with triphenylphosphine in aqueous tetrahydrofuran with the following interaction of the obtained compound with di-Boc-thiourea, hydrolysis of the obtained compound with lithium hydroxide in water dioxane and release of Boc-protection from the obtained acid with 30% solution of trifluoroacetic acid in methylene chloride.

EFFECT: obtaining intermediate products of general formula with application in the claimed method of the said reagents and conditions of reaction makes it possible to carry out the process more purposefully, reduce the quantity of side products and in that way simplify the process of obtaining and separation of the compounds.

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FIELD: chemistry.

SUBSTANCE: invention relates to field of organic chemistry, in particular to method of obtaining 1-azido-2-ethyl-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1) , which can be applied as donor-acceptor system, imitating photosynthesis, which transform sunlight into electric energy, generating active forms of oxygen, capturing radials (antioxidants), as well as demonstrating semi- and superconductive properties. According to claimed method fullerene C60 interacts with diethylaluminiumazide (Et2AlN3), taken in molar ratio C60:Et2AlN3=1:(40-60), in solution of dry toluene at -20°C in atmosphere of argon with the following heating to 40°C for 2-4 h.

EFFECT: method makes it possible to obtain novel 1-azido-2-ethyl-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1) with output to 22%.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry and specifically to a method of producing 1-bromo-2-azido-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1), which can be used as a complexing agent, a sorbent and a biologically active compound, as well as in production of novel materials with given properties. The method includes reacting fullerene C60 with bromine azide (BrN3), generated in situ from N-bromosuccinimide (NBS) and trimethylsilyl azide (TMSN3) in the presence of triflates of lanthanides and copper M(OTf)n (M=La, Sm, Yb, Cu; n=2, 3), with molar ratio C60:NBS:TMSN3:M(OTf)n=0.042:(0.042-0.063):0.754:0.042. The reaction is carried out at room temperature (about 20°C) in dry chlorobenzene for 1-4 hours under a current of dry argon without access to daylight.

EFFECT: disclosed method enables to obtain 1-bromo-2-azido-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1) with output of up to 30%.

1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry, specifically to a method of producing 1-azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene of formula (1) , which can be used as a complexing agent, sorbent and biologically active compound, as well as in production of novel materials with given properties. The method includes reacting fullerene C60 with tributyltin azide (n-Bu3SnN3) in the presence of a stoichiometric amount of Cu(OTf)2. The molar ratio C60:n-Bu3SnN3:Cu(OTf)2 is equal to 1:(1-5):(0.5-2). The reaction is carried out in a solution of dry chlorobenzene at 100°C in an argon atmosphere. The disclosed method enables to obtain 1-azido-2-butyl-1,2-dihydro(C60-Ih)[5,6]fullerene (1) with output of up to 30%.

EFFECT: improved method.

1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: method includes reacting an adamantane derivative with an inorganic azide in a solvent. The adamantane derivative used is 1,3-dehydroadamantane and the inorganic azide is an anhydrous hydrogen azide solution in diethyl ether obtained in advance. The process takes place in diethyl ether at 20-40°C and molar ratio of 1,3-dehydroadamantane:hydrogen azide of 1:2-2.7, for 10-20 minutes.

EFFECT: method enables to obtain a 1-azidoadamantane in mild conditions with high output.

2 ex

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