2,3-dialkyl-7,8-benzo-1,6-naphtiridine preparation catalyst

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst consists of complex [Sm(NO3)5][C5H5NH]2 constituted by samarium nitrate, pyridine, and nitric acid taken in molar ratio 10:20:20, respectively.

EFFECT: achieved accessibility of catalyst.

1 tbl, 2 ex

 

The invention relates to the field of catalysts, in particular catalysts for production of 2,3-dialkyl-5,6-benzo-1,7-naphthirydines (1), which can find application in thin organic synthesis upon receipt of physiologically active substances and antibiotics.

Famous four-part catalyst [Usmjerili, Fasilkom, Raghunandana. A method for production of alkyl(aryl)derivatives -5,6-benzo-1,7-naphthiridine. Auth. mon. No. 1766918 from 08.06.92. Bull. No. 37 (1992)] to obtain 2,3-dialkyl-5,6-benzo-1,7-naphthirydines consisting of ruthenium chloride (RuCl3), organophosphorus compounds (PR3), 2,2-dipyridyl and dimethyl sulfoxide, taken in a molar ratio of 0.9 to 1.5):(2-4):(0.5 to 1.5):(1-15), respectively. The process is conducted at a temperature of 180-190°C, the yield of the target products is 65-82%.

The disadvantage of this catalyst is its composition, in addition, organophosphorus compounds (PR3) not produced in the country, synthesize them on the basis of pyrophoric Mg-organic compounds (RMgX) and easy gidrolizuyushchie halides of phosphorus (l3in two stages.

Known three-component catalyst [Usmjerili, Fasilkom, Raghunandana, ATV, Ehiasarian, Haapanen. Synthesis naphthirydines and phenanthroline using catalysts based on transition and redkozemel the x metals. WPI. An. Ser. chem., 1992, No. 5, 1139-1144] to obtain 2,3-dialkyl-5,6-benzo-1,7-naphthirydines consisting of samarium chloride (SmCl3), triphenylphosphine (Ph3P) and dimethylformamide (DMF).

The disadvantage of this catalyst is inaccessibility Sml3and RH3R.

A new catalyst to obtain a 2,3-dialkyl-5,6-benzo-1,7-naphthirydines (1).

The proposed catalyst is available from complex [Sm(NO3)5]·[C5H5NH]2derived from samarium nitrate (Sm(NO3)3), pyridine (C5H5N) and nitric acid (NGO3), taken in the ratio 10:20:20 mmol, respectively. When a different ratio of the initial components of the complex [Sm(NO3)5]·[C5H5NN]2is not generated.

In the presence of the specified catalyst formed of 2,3-dialkyl-5,6-benzo-1,7-naphthirydines (1) outputs 48-62 per cent. The reaction is carried out in an inert atmosphere in the interaction of 3-aminoquinoline with aliphatic aldehydes (R2SNO, where R=C2H5the h3H7i-C3H7), taken in the ratio of 3-aminoquinoline: R CH2SNO=10:20 mmol, at a temperature of 150°C for 6 h in a mixed solvent of ethanol: DMF (3:1 volume) according to the scheme:

R=C2H5the h3H7i-C3H7 ; CT=[Sm(NO3)5]·[C5H5NN]2

The amount of catalyst required for the reaction is about 0.1-0.3 mmol (1-3 mol. % in relation to the original 3-aminoquinoline).

Differences between the proposed catalyst from the known

The proposed catalyst is available from complex [Sm(NO3)5]·[C5H5NH]2, which is obtained by mixing manufactured in the country Sm(NO3)3(when removing Samaria from ore - final treated with nitric acid, thereby forming samarium nitrate)produced on an industrial scale pyridine (C5H5N) and nitric acid (NGO3).

The invention is illustrated by examples

Example 1. Preparation of catalyst

In a glass reactor with a volume of ~100 ml, mounted on a magnetic stirrer, was placed 20 ml of water, 20 mmol of pyridine (C5H5N), pin with stirring, 20 mmol HNO3can withstand ~1 hour, then add 10 mmol Sm(NO3)3, stand under stirring for ~1 hour, removed under reduced pressure water prior to the formation of dry residue, which is a complex of composition [Sm(NO3)5]·[C5H5NH]2. The complex formed with almost quantitative yield.

Example 2. Synthesis of 2,3-dialkyl-5,6-benzo-1,7-naphthirydines

Receive the config catalyst, consisting of complex [Sm(NO3)5]·[C5H5NH]2taken in amount of 0.2 mmole, placed in a steel autoclave, which preloads 10 mmol 3-aminoquinoline, 20 mmol butyric aldehyde and a mixed solvent consisting of 3 ml of ethanol and 1 ml of DMF. The autoclave is heated for 6 hours at a temperature of 150°and With constant stirring, then cooled. Get 2-propyl-3-ethyl-5,6-benzo-1,7-naphthiridine (1) with the release of 57%.

An NMR spectrum1N (δ, M. D.): 1.11 (t, 3H, CH3), 1.46 (t, 3H, CH3), 1.81 (m, 2H, CH2), 2.62 (K, 2H, CH2), 3.06 (m, 2H, CH2), 7.70-9.42 (m, 6N, Ar). An NMR spectrum13With (δ, M. D.): C, t, t, t, d, s, s, d, d, d, d, s, s, d, s. M+250.

Other examples of the method are given in table 1.

Table 1
№ p/pAldehyde RCH2CHORatio

[Sm(NO3)5][C5H5NH]2: 3-aminoquinoline: R CH2SNO, mmol
The amount of catalyst relative to the 3-aminoquinoline, %The yield of 2,3-dialkyl-5,6-benzo-1,7-naphthirydines (1), %
1CH3CH2CH2SNO0.2:10:20257/td>
2"-"0.3:10:20362
3"-"0.1:10:20148
4p-Pr-CH2SNO0.2:10:20254
5i-Pr CH2SNO0.2:10:20251

Synthesis of 2,3-dialkyl-5,6-benzo-1,7-naphthirydines carried out in a mixed solvent consisting of ethanol and DMF, taken in the ratio of 3:1 (volume), at a temperature of 150°C for 6 hours in the "finger " autoclave under stirring.

Catalyst to obtain a 2,3-dialkyl-5,6-benzo-1,7-naphthirydines, characterized in that it consists of a complex [Sm(NO3)5]·[C5H5NH]2derived from samarium nitrate (Sm(NO3)3), pyridine (C5H5N) and nitric acid (HN3), taken in the ratio 10:20:20 mmol.



 

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SUBSTANCE: catalyst consists of complex [Pr(NO3)5][C5H5NH]2 constituted by praseodymium nitrate, pyridine, and nitric acid taken in molar ratio 10:20:20, respectively.

EFFECT: achieved accessibility of catalyst.

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FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst consists of complex [Pr(NO3)5][C5H5NH]2 constituted by praseodymium nitrate, pyridine, and nitric acid taken in molar ratio 10:20:20, respectively.

EFFECT: achieved accessibility of catalyst.

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EFFECT: achieved accessibility of catalyst.

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SUBSTANCE: catalyst consists of complex [Sm(NO3)5][C5H5NH]2 constituted by samarium nitrate, pyridine, and nitric acid taken in molar ratio 10:20:20, respectively.

EFFECT: achieved accessibility of catalyst.

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SUBSTANCE: catalyst consists of complex [Pr(NO3)5][C5H5NH]2 constituted by praseodymium nitrate, pyridine, and nitric acid taken in molar ratio 10:20:20, respectively.

EFFECT: achieved accessibility of catalyst.

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FIELD: organic synthesis catalysts.

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EFFECT: achieved accessibility of catalyst.

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