SU899568A1 - Process for preparing substituted oxasaphosphaspirocyclohexadienes - Google Patents

Description

The invention relates to the chemistry of organophosphorus compounds, and in particular to a method for producing substituted oxazaphosphaspirocyclohexadienones of the general formula

where R is methyl or ethyl;

X - chlorine · or bromine, which can be used as stabilizers of polymeric materials, antioxidants, biologically active preparations, and also as intermediates of organoelement synthesis.

A known method for producing spirocyclohexadienones not containing phosphorus atoms by the interaction of η-quinones with ketenimines [1].

Another known process for preparing substituted spirotsiklogeksadienonov, comprising reacting hlo ⁵ wounded with diphenyl ketone under UV irradiation and high pressure f2].

The purpose of the invention is the preparation of substituted oxazaphosphaspirocyclohexadienones.

¹⁰ The goal is achieved by the method of producing substituted oxazaphosphaspirocyclohexadienones of the formula I, which consists in the fact that dialkylisocyanatophosphite ¹⁵ is reacted with an equimolecular amount of halogenanil at 7080 ° C in benzene.

The reactions of trialkylphosphites with p-chi-nons proceed according to the 1-addition scheme with the formation of phosphate esters _{with the} form of an acid. Under the action of triisopropylphosphite on chloranil, all four chlorine atoms are replaced by the Arbuzov reaction with the formation of phosphonate structure products.

When dialkylisocyanatophosphites are used as a trivalent phosphorus derivative, the reaction proceeds according to the type of 1,3'-cycloaddition, which allows one to obtain a new type of compounds of the spiran structure containing both cyclohexadienone and oxazaphospholen rings, which expands the range of organophosphorus compounds.

Example 1. Obtaining 2-2-dimethoxy-6,7,9,1O-tetrachloro-1-oxa ~ 3-aza-2-phosphaspiro-4,5 ~ deca-6,9-diene-4,8-dione .

A mixture containing 3 g of chloranil and 1.86 g of dimethylphosphoric acid monoisocyanate in 30 ml of benzene is heated at 80 ° C for 4 hours. After removing the solvent, the precipitate is washed repeatedly with ether. Received 2,2-dimethoxy-6,7,9,10-.tetrachloro-1-oxa-3 ~ aza-2-phosphaspiro-4,5-deca _ό ~ 6, 9 Dien-4,8-dione (62? ); so pl. 107 S.

Elemental analysis:

Calculated,?: C 28.34; H, 1.57; P, 8.13;

C ₉ H ₆ C1 ₄ M0 ^ P.

Found,?:. C, 28.25; H 1.93; p 8.13.

PRI me R 2. Obtaining 2,2-diethoxy-6,7,9,10, -tetrachloro-1-oxa-3 ^_ aza-2-phosphaspiro-4,5-deca-6,9 ~ diene 4,8-dione.

A mixture containing 3.44 g of diethylphosphorous acid monoisocyanate and 5.19 g of chloranil in 35 ml of benzene is heated at 80 ° C. for 6 hours. After removal of the solvent, the precipitate is washed repeatedly with ether. Received 2,2-diethoxy-6,7,9,10-tetrachloro-1-oxa-3 ~ aza-2-phosphaspiro-4,5'-Deca-6.9 ^- Dien-4,8-dione (66?) ·, So pl. 132135 ° C.

Elemental analysis:

Calculated,?: C 32.27; H 2.44;

P 7.58.

Found,?: C, 31.90; H 2.39;

H, 7.77.

Example 3. Preparation of 2,2-dimethoxy-6,7,9,10-tetrabrom-1-oxa-3-aza-2-phosphaspiro-4,5-deca-b, 9 ~ -diene-4,8-dione.

899568 4

A mixture containing 2.69 g of dimethylphosphoric acid monoisocyanate and 8.44 g of bromanil in 30 ml of benzene is heated at 80 ° C. for 4 hours.

After removal of solvent, the precipitate was washed repeatedly with ether. Received 2,2-dimethoxy-6,7,9,10-tetrabrom-1-oxa-3'aza-2-phosphaspiro-4,5-deca-6,9 ”Dien-4,8-dione (65%) ; mp. 158-

161 ° C.

Elemental analysis: ..

Calculated,?: C 19.32 *, H 1.07}

P 5.54.

C ^ Br ₄ BUT ₅ P

Found,?: C, 18.79; H 1.09;

P 5 ^ 54.

Example ¹ !. Preparation of 2,2-diethoxy-6,7,9,10-tetrabrom-1-oxa. -3'aza-2-phosphaspiro-4,5-deca-b, 9 ~ -diene-4,8-dione.

A mixture containing 1.12 g of diethylphosphorous acid monoisocyanate and 2.91 g of bromanil in 30 ml of benzene is heated at 80 ° C for 6 hours. After removal of the solvent, the precipitate is washed repeatedly with ether. Received 2,2-diethoxy-b, 7,9,10-tetrabrom-1-oxa-3-aza-2-phosphaspiro-4,5-deca30 -6, d-diene-4,8-dione (68?) ; mp 1885188 ° C.

Elemental analysis:

Calculated,?: C 22.40; H 70; P 5.28.

Found,?: C, 22.64; H 1.86;

P 5.24.

The structure of the obtained compounds is confirmed by the data of elemental analysis, PC-, NMR ^m E> ~ and H-spectroscopy.

In the IR spectra there are bands (Ό, cm- ¹ ): 1050 (P-O-C);

1320 (P = N); 1720-1740 (C = 0). In the NRM ^ P spectrum, there is a +17 ppm signal

The PMR spectrum of 2,2-dimethoxy-6,7,9,10-tetrachloro-1-oxa-3-aza-2-phosphaspiro-4,5'-Deca-6.9 ~ Dien-4,8-dione contains a signal (SR ₅ COOH, 100 MHz): <G (0CH ₃ ) 4.28 and 4.40 pJ (PH) 12 Hz]. At D ⁵⁰ result hydrolysis products isolated tetrachloro (bromo) -gidrohinony constants which correspond to the known data.

^{35 The} proposed method is characterized by simple technology, the availability of ⁴ source reagents and allows you to get the target product with a yield of 62-68 ?.

899568 6

Claims (2)

by the Arbuzov reaction with the formation of phosphonate products. When dialkyl isocyanatophosphites are used as a three valence phosphorus derivative, the reaction proceeds according to type 1 «3-Cyclo-addition, which allows obtaining a new type of compounds of spira- nium structure, containing both cyclohexadienone and oxazaphospholenic cycles, which expands the range of phosphorus compounds. PRI me R 1. Obtaining 2-2-dimethoxy-6, 7,9,10-tetrachloro-1-oxa 3-aza-2-phosphaspiro-, 5-deca-6,9-diene-4, 8 -dione. . A mixture containing 3 g of chloranil and 1.86 g of dimethylphosphorous acid monoisocyanate in 30 ml of benzene is heated for an hour. After the solvent has been removed, the precipitate is washed several times with ether. 2,2-Dimethoxy-6,7,9,10-tetrachloro-t-oxa-3-aza-2-phosphaspiro-4, 5-deca-6,9-diene - (, 8-dione (62%) was obtained ; mp. 107 Elemental analysis: Calculated,%: C 28, H 1, C7, P 8.13: Found,%: -C 28.25; H 1.93; P 8.13. e p 2. Preparation of 2,2-diethoxy-6, 7,9,10, -tetrachloro-1-oxa-3-aza-2-phosphaspiro-, 5-deca-6,9DI en-A, 8-dione. A mixture containing G, g of monoiso cyanate, diethylphosphorous acid and 5.19 g of chloranil in 35 ml of benzene is heated at 8 ° C for 6 hours. After removing the solvent, the precipitate is repeatedly washed with ether. 2.2-Diethoxy-6,7,9, 10-tetrachlo -1 -ox-3-aza-2-phosphaspiro-4,5-deca-6,9-diene-4,8-dione (66), mp 1 32 135С. Elemental analysis: Calculated: С 32.27; H 2 ;; Р 7.58. Cf, b, oCl4N (VP Found; С 31.90; H 2.39; H 7.77. P p and measure 3. Preparation of 2,2-dimethoxy-6, 7,9,10-tetrabromo 1-oxa-3-aza-2-phosphaspiro-4,5-deca-6,9-di-, 8- Dion. A mixture containing 2.69 g of dimethylphosphorous acid monoisocyanate and 8, kh g of bromoanil and 30 ml of benzene is heated at C for hours. After removing the solvent, the precipitate is repeatedly washed with ether. Received 2,2-dimethoxy-6,7,9, Yu-tetrabromo-1-oxa-3-aza-2-phosphaspiro-4, 5-deca-6, 9-diene-4,8-dione (b5%) ; m.plL581 .61C. Elemental analysis:., Calculated ,: С 19,32; H 1.07, P 5.5. CghigBr fJOgP Found: C, 18.79; H 1.09; R 5.5. Example, Preparation of 2,2-diethoxy-6, 7,9,10-tetrabrom-1-oxa-. -Z-aza-2-phosphaspiro-, 5-deca-6, 9-diene-4, 8-dione. A mixture containing 1.12 g of diethylphosphorous acid monoisocyanate and 2.91 g of bromanil in 30 ml of benzene is heated at 80 ° C for 6 hours. After removing the solvent, the precipitate is repeatedly washed with ether. 2,2-DIETOXI-6,7,9, U-tetrabromo-1-oxa-3-aza-2-phosphaspiro-, 5-deca-6, 9-diene-4,8-dione (68) was obtained; m.p., 185G88 S, Elemental analysis: Calculated: С 22, “O; H 70; P 5.28. ,, P Found: С 22,64; H 1.86; P5, 2. The structure of the obtained compounds is confirmed by the data of elemental analysis, IR, and H-spectroscopy. The IR spectra contain bands (, 1050 (P – O – C); 1320 (); 1720–17 0 (). There is a signal in the spectrum +17 ppm In the PNR spectrum of 2,2-dimethoxy-6,7,9, U-tetrachloro-1-oxa-3-aza-2-phosphaspiro, 5 Deca-6,9-Dien-4,8-dione There is a signal (, 100 MHz): ((OCH-) i, 28, and C, PJ (PH) CQ 12 Hz. As a result of the hydrolysis of the products, tetrachloro (bromine) -hydroquinones are separated, the constants of which correspond to the known data. The proposed method is characterized by simple technology , availability of initial reagents and It allows to obtain the target product with a yield of 62-68%. 589956 Claim for the preparation of substituted oxazaphosphaspirocyclohexadienones of the general formula ... 5 0 where R is methyl or ethyl; X is chlorine or bromine, containing (lcyc in TOM, dialkyly) - 15 subject to 8 4 action with an equimolar amount of halogenanil at 70-8 ° C in the environment. Sources of information taken into account during the examination 1. Ogino.K. and oth. Photocycloaddltlons of p-Q, uinones to Ketenimines .- I.Chem. Sec., Perkln. Trans, 1979, p. 1552. 2, Ogino K. and oth. Photo-Indiiced Cucloadd of Tetra-p-Quinones to Diphenylketen.I .Chem. Soc., Chem. Coom, 1979, IJ, p.