RU2434839C2 - METHOD OF PRODUCING (C60-Ih)[5,6]FULLERO[2',3':1,9]-CYCLOPROPAN-1'-YL(CYCLOALKYL)METHANONES - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing (C₆₀-I_h)[5,6]fullero[2',3':1,9]cyclopropan-1'-yl(cycloalkyl)methanones of general formula (1):

n=1; 2; 3, which can be used as components of high-energy fuels, as well as nanomaterials for preparing modern additives for heavily loaded mechanisms and machines and starting substances in production of medicinal agents. The method involves reaction of C₆₀-fullerene with 2-oxo-2-cycloalkyl diazoethanes (N₂CHC(O)cycloalkyl) in o-dichlorobenzene (o-DCB) in the presence of a three-component catalyst {Pd(acac)₂ : 2PPh₃:4Et₃Al}, taken in molar ratio C₆₀:2-oxo-2-cycloalkyl diazoethane:Pd(acac)₂:PPh₃:Et₃Al = 0.01:(0.03-0.07):(0.001-0.003):(0.002-0.006):(0.004-0.012), preferably 0.01:0.05:0.002:0.004:0.008, at temperature 80°C for 0.5-1.5 hours.

EFFECT: method enables to obtain desired products with high output.

1 tbl, 9 ex

Description

The invention relates to the field of organic synthesis, and in particular to a method for producing (C ₆₀ -I _h ) [5,6] fullero [2 ', 3': 1,9] cyclopropan-1'-yl (cycloalkyl) methanones of the general formula (1 )

Methanofullerenes can be used as components of high-energy fuels, as well as nanomaterials for the manufacture of modern additives for highly loaded mechanisms and machines, starting materials in the synthesis of drugs (L.N. Sidorov, M.A. Yurovskaya, A.Ya. Borschevsky, I. V. Trushkov, I. N. Ioffe. Fullerenes: Textbook. M.: Publishing house "Examination", 2005, 688 S. [1]).

A known method (Y. Nakamura, K. Inamura, R. Oomuro, R. Laurenco, TTTidwell, J. Nishimura. Org. Biomol. Chem., 2005, 3, 3032 [2]) to obtain (C ₆₀ -I _h ) [ 5,6] fullero [2 ', 3': 1.9] cyclopropan-1'-yl (aryl) methanones (2) in a mixture with the corresponding isomeric 5,6-open adducts (3) and (4) with a total yield less than 30% (1: 1: 3 ratio, respectively) by the reaction of C _60- fullerene (5) with aryldiazoketones (6) at a temperature of 20 ° C for a week.

The disadvantage of this method is the low yields of the formation of the target cycloducts and the selectivity of the reaction. The proposed method cannot selectively obtain (C ₆₀ -I _h ) [5,6] fullero [2 ', 3': 1,9] cyclopropan-1'-yl (cycloalkyl) methanones of the general formula (1).

A known method (R. Pellicciari, B. Natalini, TVPotolokova, M. Marinozzi, MNNefedova, ASPeregudov, VISokolov. Synthetic Commun., 2003, 33, 903 [3]) selective production (C ₆₀ -I _h ) [5,6] fullero [2 ', 3': 1.9] cyclopropan-1'-yl (cymantrenyl) methanone (7) with a yield of ~ 20% by reaction of C _60- fullerene (5) with diazoacetylcimantrene at room temperature in the presence of stoichiometric amounts of the Rh ₂ complex (OAc) ₄ .

The disadvantage of this method is the use of expensive and inaccessible Rh-complex in stoichiometric quantities, as well as the low yield of the formation of the target 6.6-closed adduct, which leads to high economic costs.

A new effective method for the preparation of (C ₆₀ -I _h ) [5,6] fullero [2 ', 3': 1,9] cyclopropan-1'-yl (cycloalkyl) methanones (1) is proposed.

The essence of the method consists in the interaction of fullerene (C ₆₀ ) with 2-oxo-2-cycloalkyl diazoethanes (N ₂ CHC (O) cycloalkyl) in o-dichlorobenzene (o-DCB) in the presence of a three-component catalytic system {Pd (acac) ₂ : 2PPh ₃ : 4 Et ₃ Al} taken in a molar ratio of C ₆₀ : diazo compound: Pd (acac) ₂ : PPh ₃ : Et ₃ Al = 0.01: (0.03-0.07) :( 0.001-0.003) :( 0.002-0.006) :( 0.004-0.012), preferably 0.01: 0.05: 0.002: 0.004: 0.008, at a temperature of 80 ° C for 0.5-1.5 hours. Receive (C ₆₀ -I _h ) [5,6] fullero [2 ', 3': 1 , 9] cyclopropan-1'-yl (cycloalkyl) methanones with a yield of 44-68%. The reaction proceeds according to the scheme.

Carrying out the specified reaction in the presence of a palladium catalyst [Pd] of more than 20 mol% with respect to fullerene C ₆₀ does not lead to a significant increase in the yields of the target products (1). The use of a palladium catalyst [Pd] in an amount of less than 20 mol% with respect to fullerene C ₆₀ reduces the yield of the target product, which is associated with a decrease in reaction centers. The reaction should be carried out at a temperature of 80 ° C. The reaction at a higher temperature (for example, 110 ° C) is associated with an increase in energy consumption, at a lower temperature (for example, 40 ° C), the reaction rate decreases.

Significant differences of the proposed method.

The proposed method is based on the use of a palladium complex in catalytic amounts. In the known method, the Rh complex is used in stoichiometric amounts.

The method is illustrated by examples.

To a solution of 0.002 mmol Pd (acac) ₂ in 0.5 ml of o-DCB in a stream of dry argon at a temperature of -5 ° C and stirring, add 0.004 mmol of PPh ₃ , 0.008 mmol of Et ₃ Al and 0.01 mmol of C ₆₀ -fullerene in 1 ml of o- DHB. The reaction mass is heated to 80 ° C and 0.05 mmol of 2-oxo-2-cycloalkyl diazoethane (N ₂ CHC (O) cycloalkyl) in 0.5 ml of o-DCB is added dropwise. After 1 h, the reaction mass is cooled and passed through a column with a small layer of silica gel. Receive (C ₆₀ -I _h ) [5,6] fullero [2 ', 3': 1,9] cyclopropan-1'-yl (cycloalkyl) methanones with a yield of 44-68% (according to HPLC).

Spectral characteristics (1)

¹ H NMR spectrum (δ, ppm, J / Hz): 1.15-1.40 (m, 4H, 2CH ₂ ,), 2.62-2.71 (m, 1H, CH), 5.19 (s, 1H, CH). ¹³ C NMR spectrum (δ, ppm): 12.99 (C ^6.7 ), 22.66 (C ⁵ ), 46.60 (C ³ ), 72.42 (C ^1.2 ), 190.02 (C ⁴ ). The signals of the carbon atoms of the fullerene fragment are located in the region of 130-150 ppm. Mass spectrum (MALDI-TOF), calculated: 802.743, found: 802.734. Spectral characteristics (2)

¹ H NMR spectrum (δ, ppm, J / Hz): 2.00-2.80 (m, 6H, 3CH ₂ ), 3.96-4.09 (m, 1H, CH), 4.94 (s, 1H, CH). ¹³ C NMR spectrum (δ, ppm): 18.73 (C ⁷ ), 25.08 (C ^6.8 ), 43.86 (C ³ ), 47.52 (C ⁵ ). 72.07 (C ^1.2 ), 190.06 (C ⁴ ). The signals of the carbon atoms of the fullerene fragment are located in the region of 130-150 ppm. Mass spectrum (MALDI-TOF), calculated: 816.769, found: 816.734. Spectral characteristics (3) ¹ H NMR spectrum (5, ppm, J / Hz): 1.50-2.35 (m, 8H,

4CH ₂ ), 3.30-3.45 (m, 1H, CH), 5.06 (s, 1H, CH). ¹³ C NMR spectrum (δ, ppm): 26.65 (C ^7.8 ), 29.29 (C ^6.9 ), 45.29 (C ³ ), 47.39 (C ⁵ ), 72.39 (C ^1.2 ), 190.53 (C ⁴ ). The signals of the carbon atoms of the fullerene fragment are located in the region of 130-150 ppm. Mass spectrum (MALDI-TOF), calculated: 830.796, found: 830.812.

Other examples confirming the method are given in table 1

Table 1 No. p / p The molar ratio of C ₆₀ : N ₂ CHC (O) cycloalkyl: Pd (acac) ₂ : PPh ₃ : Et ₃ Al, mmol Reaction time, hour The yield of target products,% R = cyclo-Pr one 0.01: 0.05: 0.002: 0.004: 0.008 one 58 2 0.01: 0.07: 0.002: 0.004: 0.008 one 61 3 0.01: 0.03: 0.002: 0.004: 0.008 one 53 four 0.01: 0.05: 0.003: 0.006: 0.012 one 68 5 0.01: 0.05: 0.001: 0.002: 0.004 one 44 6 0.01: 0.05: 0.002: 0.004: 0.008 1.5 62 7 0.01: 0.05: 0.002: 0.004: 0.008 0.5 51 R = cyclo-bu 8 0.01: 0.05: 0.002: 0.004: 0.008 one 56 R = cyclo-Pentyl 9 0.01: 0.05: 0.002: 0.004: 0.008 one fifty

The reaction was carried out at a temperature of 80 ° C in o-dichlorobenzene.

Claims (1)

The method of obtaining (C ₆₀ -I _h ) [5,6] fullero [2 ', 3': 1,9] cyclopropan-1'-yl (cycloalkyl) methanones of the general formula (1):

characterized in that C ₆₀ fullerene reacts with 2-oxo-2-cycloalkyl diazoethanes (N ₂ CHC (O) cycloalkyl) in o-dichlorobenzene (o-DCB) in the presence of a three-component catalyst {Pd (acac) ₂ : 2РРh _3: 4Et ₃ Al} taken in a molar ratio of C ₆₀ : 2-oxo-2-cycloalkyl diazoethane: Pd (acac) ₂ : PPh _3: Et ₃ Al = 0.01: (0.03-0.07) :( 0.001 -0.003) :( 0.002-0.006) :( 0.004-0.012), preferably 0.01: 0.05: 0.002: 0.004: 0.008, at a temperature of 80 ° C for 0.5-1.5 hours