SU1318587A1 - Method for producing n,nъ-disubstituted 1,8-deminonaphthalenes - Google Patents

Abstract

The invention relates to aromatic amines, in particular to the preparation of N, N-disubstituted 1,8-diaminonaphthalenes (AH), substituted in the amino groups a) R, R2-CHj; b) R, -CH,. ; c) R, -CH ,, d) R,. Rj-CH CgHy, which can be used in organic synthesis. Simplification of the process, an increase in the yield of AH and the expansion of their range are achieved by using other raw materials. The preparation of AN is carried out by cleavage of the corresponding K, s-displaced perimidones with powdered fused alkali or with sodium amide in an environment of absolute dimethylaniline in a dry nitrogen atmosphere. The method provides the preparation of AN in two stages with a total yield of 95%, versus 607o by a known method, as well as the preparation of previously unknown AN (i.e., b, c, d). From sl U) eo IUI 00

Description

one

The invention relates to an improved method for producing K, M-disubstituted, 8-diaminonaph-jjHHOB of the general formula

where R R2 is CHj; 1a)

C;

R, - CH,

R,;

R CH5 R CHjt- gH

R.

Rj -, -,

(Ir),

(sixteen) ,. (Ib)

which can be used in organic synthesis, in particular in obtaining perikondensirovannyh heterocyclic systems.

The purpose of the invention is to simplify the process, increase the yield and expand the range of target N, N-disubstituted, 8-diaminonaphthalenes.

Example 1. 1,8-Bis (methyl amino) naphthalene (1a),

1,3-dimethylperimidone. A mixture of 3.7 g (0.02 mol) of perimidone, 2.8 g (0, OA mol) of powdered 80% KOH and 150 ml of acetone is stirred for 15–20 minutes, and the resulting suspension is added to the resulting suspension for 20 minutes. A solution of 5.68 g (0.04 mol) of methyl iodide in 20 m of acetone is added, after which stirring is continued at room temperature for an additional 3 hours. Then all the acetone is distilled off from the reaction mixture, the residue is treated with 300 ml of water. The precipitate formed is filtered off, washed with water and pre-crystallized from alcohol or aqueous alcohol. Obtain 3.5 g (83%), 3-dimethylperimidone in the form of small white crystals t, pl. 208-209 ° C, which corresponds to the literature data.

1,8-Bis (methylamino) naphthalene (1a) (method A),

A mixture of 7 g (0.008 mol) of 1,3-dimethylperimidone, 8 ml of absolute dimethylaniline and 2.4 g (0.06 mol) of powdered sodium amide is stirred under dry nitrogen at room temperature for 15 minutes. Then the reaction mass is heated. to 170-190 ° C and kept at this temperature for 3 hours, continuing to mix and pass nitrogen. After cooling the mixture, 10 ml of water are carefully introduced into the mixture to destroy the unreacted sodium nitride; during this operation the mixture is cooled to

185872

bath with ice and salt. After adding water to the mixture, 30 ml of sulfuric ether are introduced, filtered, the ether layer is separated) the aqueous layer is extracted 5 times with ether (40 ml). The ether extracts are combined, the ether is distilled off, and the residue x is distilled off with water vapor: dimethylaniline is distilled off. The residue is a thick reddish oil, which solidifies on cooling. The crystals are filtered and recrystallized from aqueous alcohol. Obtain 1.3 g (87%) 1p8-bis (methylamino) naphthalene in the form of t5 pale yellow crystals, so pl. 101 sec ,, which corresponds to the literature data

1,8-Bis (methylamino) naphthalene (1a) (method B),

20 A mixture of 2 g (0.009 mol) of 1,3-dimethylperimidone and 2.5 g (0.04 mol) of finely ground anhydrous (fused) caustic potassium is heated in a stream of dry nitrogen at 200–210 ° C for 3 h. On cooling to room temperature, the vessel with the melt is placed in a bath with ice and salt, and the mixture is triturated with 70 ml of water. The precipitate is filtered off, 30 washed with 100 ml of water and dried in a vacuum desiccator over potash. The crude product is recrystallized from aqueous alcohol to obtain 1.67 g (97%) of 1,8-bis (methylamino) naphthalene J5 (1a) as yellowish crystals, t, pl,. For all spectral characteristics, the compound is identical to a notorious sample.

Example 2, 1-Methylaminr-8-40 ethylaminonaphthalene (16),

1-Methyl-3-ethylperimidone. To a suspension of 3.5 g (0.018 mol) of 1-methylperimidone and 3.5 g (0.05 mol) of finely ground 80% caustic 45 potassium in 130 ml of acetone, with stirring, a solution of 5.5 g ( 0.05 mol) of ethyl bromide in 20 ml of acetone. The mixture was stirred at room temperature for 50 2 hours, after which the acetone was distilled off, and 200 ml of cold water was added to the residue. The resulting residue is filtered, washed with water (75 ml) and dried in air or in a vacuum j desiccator. After recrystallization from aqueous alcohol, 3.0 g (75%) of 1-methyl-3-ethylperimidone are obtained in the form of small white crystals, m.p. 12-114 seconds

IR Spectrum (CCl), :)., Cm-: 1673.

Found,%: C 74.1; H 6.2; N 12.6.

C ,,, 0.

Calculated,%: C, 74.3; H 6.2; N 12.4.

1-Methylamino-8-ethylaminonaphthalene (16).

The reaction of 1.6 g (0.007 mol) of 1-methyl-3-ethylperimidone and 2.5 g (0.045 mol) of crushed anhydrous KOH, as well as the selection of the reaction product, was carried out as described in Example 1 (method B). The half-given in example 1 for compound 1a (method A),

Isolation of the reaction product is carried out as follows. After distilled 5 dimethylaniline with steam, the remaining dark thick oil is extracted with benzene (3 times 25 ml). The benzene extract is evaporated to a volume of 15 ml and passed through a column with III alumina using benzene as eluent. Collect the first fraction, painted in a reddish color. The benzene is distilled off in a vacuum at the addition of a pump, leaving

1.3 g (92%) of 1-methylamine-8-ethyl-J5 ke 2.1 g (80%) of 1-methylamino-8-benamino-naphthapine (16) in the form of colorless zilaminonaphthalene in the form of thick crystals, t. yl 74-75 C (from aqueous alcohol).

 3380,

IR (CHCl1), 9NH 3287.

PMR spectrum (CCl4), S, MD: 1.17 (t., 3N, N-CHjCH); 2.68 (s., N, N-CH,); 2.94 (q, 2H,,); 5.18 (broad s., 2H, NHx2); 6.60 (m, 2H, H-2.7); 7.04 (m., 4H, H-3-6).

Found,%: C 77.2; H 7.8; N 13.5;

reddish oil.

IR spectrum (CC1), „, .338 3300.

20

25

Spectrum PMR (SS), ppm: 2.7 (s., 3N, N-CHj); 4.15 (s, 2H, N-CHj.); 5.52 (broad s., 2H, Shh2); 6.37 (m, 2H, H-2.7); 7.12 (m., 9H, H-3-6,).

Example 4. 1,8-Bis (benzyl-amino) naphthalene (1g).

1,3-Dibenzylperimidone.

Cj, H, 6N ,.

; C, 78.0; H 8.0; 3. 1-Methylamino-8. Interaction of 3.7 g (0.02 mol) perimidone, 2.8 g (0.04 mol) of powdered 30% 80% KOH and 5.1 g (0.04 mol) of chloride benzyl in 150 ml of acetone is carried out as described in Example 1. 6 g (79%) of white crystals of 1,3-di-calcined N 14.0 are obtained.

Example benzylaminonaphthalene (1c).

1-Methyl-3-b. Benzylperimidone, Interaction 3 g (0.015 mol) of 1-methyperperidine, 3.8 g (0.03 mol) 5 benzylperimidone, so pl. 190-19GS, benzyl chloride and 2.1 g (0.03 mol), which corresponds to the literature data — 80% KOH in 70 ml of acetone, as well as. However, the reaction product is selected according to the procedure described in Example 1 for 1,3-dimethylperimidone. 40 3.8 g (87%) of 1-methyl-3-benzylperimidone are obtained, which is purified by recrystallization from octane, colorless needles, mp. 126 ° C.

45 example 1 for the synthesis of compounds

IR spectrum (СНС1,) :) cm L 1670. la (method A). 2.5 g (7%) are obtained.

colorless crystals, so pl. 115-116 ° C (from aqueous alcohol).

IR (CHCl 2), jj, 50 3360, 3280.

PMR spectrum (SSHD),, ppm: 4.0

1, 8-Bis (benzylamino) naphthalene (1g

The interaction of 3.6 g (0.01 mol) of 1, 3-dibenzylperimidone and 2.4 g (0.06 mol) of finely divided sodium amide in 10 ml of absolute dimethyl-aniline and the isolation of the reaction product is carried out according to the procedure given in

Found,%: C 79.3; H 5.4; N 10.0,

C ,, H ,, N, 0.

:: 79.1; H 5.6;

Calculated N 9.7.

1-Methylamino-8-benzylamine naphthalene (IB),

(d, 4H, N — CH, X 2); 5.57 (m, 2H, Shh2); 6.32 (m., 2H, H - 2.7); 7.02 (m, 14H, H-3-6, X 2).

The reaction of 2.9 g (0.01 mol) of 1-methyl-3-benzylperimidone, 2.4 g (0.06 mol) of finely divided sodium amide in 8 ml of absolute dimethylaniline was carried out according to the procedure.

318587. four

Example 1 for Compound 1a (Method A)

Isolation of the reaction product is carried out as follows. After distillation of 5 dimethylaniline with steam, the remaining dark thick oil is extracted with benzene (3 times 25 ml). The benzene extract is evaporated to a volume of 15 ml and passed through a column with III alumina, using benzene as eluent. Collect the first fraction, painted in a reddish color. The benzene is distilled off in a water jet vacuum, yielding 2.1 g (80%) of 1-methylamino-8-benzylaminonaphthalene in the form of a thick

reddish oil.

IR spectrum (CC1), „, .3380, 3300.

Spectrum PMR (CC), ppm: 2.7 (p., 3N, N-CHj); 4.15 (s, 2H, N-CHj.); 5.52 (broad s., 2H, Shh2); 6.37 (m, 2H, H-2.7); 7.12 (m., 9H, H-3-6,).

Example 4. 1,8-Bis (benzyl-amino) naphthalene (1g).

1,3-Dibenzylperimidone.

The reaction of 3.7 g (0.02 mol) of perimidone, 2.8 g (0.04 mol) of powdered 80% KOH and 5.1 g (0.04 mol) of benzyl chloride in 150 ml of acetone is carried out according to the method described in example 1. Get 6 g (79%) of white crystals of 1,3-dibenzylperimidone, so pl. 190-19GS, which corresponds to literary data.

benzylperimidone, t. pl. 190-19GS, which corresponds to literary data.

1, 8-Bis (benzylamino) naphthalene (1 g).

The interaction of 3.6 g (0.01 mol) of 1, 3-dibenzylperimidone and 2.4 g (0.06 mol) of finely divided sodium amide in 10 ml of absolute dimethyl-aniline and the isolation of the reaction product is carried out according to the procedure given in

2); 5.57 (m, 2H, 2H, H - 2.7); 7.02 x 2).

85.0; H 6.4;

C ,, H ,, N,

Calculated,%: C 85.2; H 6.5; N 8.3.

 The original perimidones are very accessible. Symmetric compounds are obtained in two stages with a total yield of 5-95%, while, according to a known method, the starting perimidinium salts are obtained with a yield of 60%.

Thus, the proposed method allows to obtain the desired product (1a) with a higher yield, as well as a number of its previously unknown derivatives (16) - (1g).

Formula 3: on a b in t

f. A method of producing N, N-disubstituted 1,8-diaminonaphthalenes of the general formula

by splitting N, N derivatives of disubstituted perimidines with an alkaline agent when heated, characterized in that, in order to simplify the process, increase the yield of target products and expand their range, N, N -disubstituted perimidones of the general formula are used as derivatives of perimidines

de R,

R, R, R,

 one

- Rj,

R, - CH

gsbn

7 5

where R, and RJ have the indicated meanings, which are reacted with powdered fused alkali in a dry nitrogen atmosphere or with sodium amide in an absolute dimethylaniline medium in a dry nitrogen atmosphere.

Compiled by L. Ioffe. Editor V, Petrash Tehred N. Glushchenko Proofreader M. Demchik

Order 2478/21 Circulation 371 Subscription

VNIIPI USSR State Committee

for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5

Production and printing company, Uzhgorod, st. Project, 4

Claims (1)

The method of obtaining Ν, Ν-disubstituted 1,8-diaminonaphthalenes of the general formula by splitting the derivatives of Ν, Ν * disubstituted perimidines with an alkaline agent when heated, characterized in that, with the aim of 5 to simplify the process, increase the yield of target products and expand their assortment, Ν, Ν’-disubstituted perimidones of the general formula are used as derivatives of perimidines OU-NHRi where R, = R _t - SI ,, R is CH ₃ ; R ₂ - C _g H ₃ ; R is —CH ₃ ; R ₂ - CH ₂ C ₆ H ₄ , R, = R ₂ - CH ₂ C ₆ H ₆ , 20 where R ₍ and R ₂ have the indicated meanings, which are introduced into interaction with powdered fused alkali in an atmosphere of dry nitrogen or with sodium amide in a medium of absolute dimethylaniline in an atmosphere of dry nitrogen,