DE1257153B - Process for the preparation of new basic esters of phosphorous, phosphonic or phosphinous acid - Google Patents

Description

Process for the production of new basic esters of phosphorous, phosphonous or phosphinous acid It has been found that new basic esters can be used the phosphorous, phosphonic or phosphinous acid of the general formula (Z) rnP [O - R (NHR,), I, where R is an inert aliphatic or inert aromatic radical and R1 denotes hydrogen, an alkyl or an alkylene radical, Z denotes an inert one is an organic residue that is bonded to phosphorus directly or via oxygen, m is a number from 0 to 2, n is a number from 1 to 2 and p is a number from 1 to 3, obtained when one phosphorous, phosphonous or phosphinous acid chlorides, esters or -amides with corresponding amino alcohols or aromatic hydroxyamines, their Amino groups still contain at least one reactive hydrogen atom.

It is surprising that these new esters of phosphorous acid, phosphonous acid and phosphinous acid, which are still primary or secondary Contain amino groups in the molecule, are viable or under the reaction conditions, which are explained in more detail below, no side reactions such as N-alkylations, Ring closure reactions, etc. suffer.

It is well known that z. B. orthophosphoric acid esters are very good alkylating agents for amines. So you get, for example, with the implementation of triethyl phosphate Ammonia ethylamine (W. G e r r a r d and G. J. Jeacocke, Chem. And Ind., 1954, [1538]) and of tributyl phosphate with aniline N, N-dibutylaniline (J.H. Billmann, A. Radike and B. W; M u n d y, Am. Soc., 64, p. 2977 [1942]).

This N-alkylation by phosphoric acid esters is also smooth like the same reactions with sulfuric acid esters.

It is further surprising that the phosphorous acid esters do not show this reaction behavior, since, for example, the esters of the sulphurous Acids can be used very well for the alkylation of amines (cf. B. H o u b e n W e y 1, Methods of the org. Chemie, Vol. 11/1 p. 214).

The formation of alkylenimines from the Phosphorous acid esters of aliphatic amino alcohols are expected. For example As is known, ethyleneimine is formed from the ethanolamine sulfuric acid ester (German Patent 665,790).

Likewise, on the basis of numerous examples known from the literature, it can be expected that, with suitable amino alcohols, ring closings to form amide esters of the type could take place or the hydroxyl-containing substituted amides would be formed.

However, all of these side reactions could occur in the implementation of the above formulated compounds of trivalent phosphorus with amino alcohols or not are observed to a negligible extent.

Phosphorus compounds suitable for the implementation are, for. B. derivatives of phosphorous acid, phosphonous acid and phosphinous acid, such as their halides, esters or amides. Of the numerous compounds of this type, only a few may be mentioned, such as further as well as P (OCH3) 3 P (oC2Hs) 3 Suitable amino alcohols are, for. B.

H2N-CH2-CH2-OH HN-CH2-CH2-OH CH3 HO (CH, kNH, H2N <CH20H H2N - OH R. H2N ¼ OH H2N 4 OH NH2 R = alkyl, OR, Cl, SQ-R H N- (CH, OH CH2CH = CH2 NH2-CH2-CHOH-CH2-NH2 The reaction conditions under which the new esters can be prepared can vary within certain limits and depend primarily on the type of phosphorus compound with which the amino alcohol is reacted.

So it is useful to use the above-mentioned halides Acids of phosphorus work under cooling, as these reactions are highly exothermic get lost. If you work in the absence of a hydrogen halide acceptor, you get one is equal to the hydrohalides of the corresponding amino esters, from which in many cases by treating the free ones with ammonia or other strong bases Have amino esters produced. However, you can also right at the beginning of the reaction the amount of tertiary base required to bind the hydrogen halide add and the reactions in an inert solvent such as chloroform, toluene, Perform chlorobenzene etc.

When reacting esters or amides of the acids mentioned above of phosphorus with an amino alcohol must be in the heat, and at temperatures from about 70 to 160 "C are carried out, with elimination of alcohol or secondary amine the desired compounds are obtained.

Working in a solvent is part of this implementation not necessary, but the boiling point of the amino alcohol should be as low as possible the boiling point of the phosphoric ester or amide or the boiling point of the split-off Alcohol or amine are removed, otherwise poorer yields are obtained. Catalysts are generally not required for the reaction.

The compounds according to the present invention are valuable intermediates for the production of phytosanitary products, e.g. B. insecticides, of flame retardants and plastics.

The procedure is illustrated by the examples set out below explained.

Example 1 Preparation of tris (p-aminoethyl) phosphite a) From PCl3 and ethanolamine in a solution of 185 g (3 mol) of ethanolamine in 11 chloroform 137.5 g (1 mol) of PCl3 were added dropwise with stirring at -20 to 00C and then dry ammonia gas introduced. The Nf-hC1 formed is suctioned off.

The solution is left to stand overnight, with a small Amount of a black amorphous precipitate deposited. After filtration and evaporation of the chloroform are 169 g (80 ° / Q of theory) tris (p-aminoethyl) phosphite in colorless crystal needles with a melting point of 103 to 105 "C obtained.

Analysis: Calculated C 34.1, H 8.55, N 19.8, P 14.57, 0 22.8; found C 33.8, H 8.30, N 19.8, P 15.0, O 23.1. b) From phosphorous acid tris (diethylamide) by splitting off diethylamine 248 g (1 mol) of phosphorous acid tris (diethylamide) and 185 g (3 mol) of ethanolamine are placed in the three-necked flask with a descending condenser Stir heated to 90 to 100 "C, with a vigorous elimination of diethylamine begins. The main amount of diethylamine is at normal pressure, the remainder at 10 mm Hg distilled off. On cooling the reaction mixture, 206 g crystallized (98% of theory) Tris (p-aminoethyl) phosphite in colorless needles. c) From triethyl phosphite by transesterification 166 g (1 mol) of triethyl phosphite and 183 g of dry Ethanolamine are slowly heated up while stirring. One begins at 120 to 130 ° C vigorous splitting off of alcohol. The alcohol is distilled off over a small column, up to 95 g are split off. Then the temperature is increased to 150 ° C, with a further 39 g of distillate being collected.

Finally, a vacuum is applied to terminate the reaction. It left behind 168 g of tris-t, B-aminoethyl) phosphite as a light-colored melt which crystallizes out on cooling. Yield: 79% of theory.

Example 2 representation of 327.3 g of m-aminophenol are dissolved in 2 l of chlorobenzene at 100.degree. 137.4 g of PCl3 are then added dropwise at the same temperature. After all the PCl3 has dripped in, the reaction is allowed to continue for a further 2 hours. A vigorous stream of ammonia is then passed through the hydrochloride suspension for 4 hours, the free base forming with the separation of NH4Cl. It is sucked off hot from NH4Cl and the chlorobenzene evaporated in vacuo. There remain behind 302 g (85% of theory) of white crystals. M.p. 115 to 119 ° C.

Example 3 representation of 137.4 g (1 mol) of PCl3 are added dropwise at 100 to 1100 ° C. to a solution of 370 g of 2-amino-4-oxy-1-methylbenzene in 3 l of chlorobenzene. Ammonia gas is then passed into the hydrochloride suspension for 2 hours, the free amine being formed with the separation of NH4Cl. After filtering off the NH4Cl and evaporation of the chlorobenzene weZcn 379! (950 / o of theory) Tris (3-amino-4-methyl-phenyl) -phosphite obtained in colorless crystals.

Example 4 Preparation of P [O - (CH2 - NR2] 3 A mixture of 124 g (0.5 mol) of phosphorous acid tris (diethylamide) and 175 g (1.5 mol) of 6-aminohexanol-1 is heated while stirring. Distill from the reaction mixture at 80 to 90 "C 110 g of diethylamine. The reaction is then brought to an end in vacuo. In arrears a colorless clear U1 remains. The yield is theoretical.

Analysis: Calculated. . C 57.0, H 11.1, N 11.1, P 8.2; found ... C 57.5, H 10.9, N 10.9, P 8.2.

Example 5 Preparation of P [O - (CH2 - NR2] 3 A mixture of 83 g (0.33 mol) PhosphorigsäuretrisXdiäthylamid) and 89 g (1 mol) 4-aminobutanol-1 is brought to implementation analogously to Example 4.

The reaction product is a colorless oil; the yield is theoretical. n200 = 1.4873.

Analysis: Cl2H30N3O3P (molecular weight 295) Calculated ... C 48.8, H 10.15, N 14.25, P 10.5; found . C 48.4, H 9.95, N 14.3, P 10.5.

Example 6 Representation of A solution of 179 parts of phenylphosphonous dichloride is added dropwise to a solution of 228 parts of m-aminophenol in 2000 parts of chlorobenzene. The resulting suspension is stirred for 1 hour and then dry ammonia gas is passed in at 80 to 100 ° C. until it is saturated. After filtration of the NH4Cl and evaporation of the chlorobenzene, 262 parts (81U / o) bisgm-aminophenyl phenylphosphonate are obtained as tough, non-crystallizing U1.

Analysis: Calculated ... C 66.7, H 5.2, N 8.6, P 9.6; found . C 66.5, H 5.2, N 7.9, P 10.1.

Example 7 Representation of A solution of 137.5 parts of phosphorus trichloride in a little chlorobenzene is added dropwise to a suspension of 430.5 parts of 6-chloro-3-aminophenol in 2.5 l of chlorobenzene at 90 to 1000 C with vigorous stirring. The resulting chlorohydrate suspension is stirred for a further 1 to 2 hours. At 60 to 70 ° C, dry ammonia gas is then introduced until it is saturated. The precipitated NH4.Cl is filtered off while hot and boiled twice with chlorobenzene. On evaporation of the combined filtrates, 255 parts of the above compound are obtained in the form of light gray crystals with a melting point of 1600C.

Example 8 representation of Following the procedure described in Example 7, 165 parts (46.5 u / o) of the above compound are obtained from 327 parts of o-aminophenol and 137.5 parts of phosphorus trichloride in the form of colorless crystals with a temperature of 1453C.

Example 9 Representation of 96.5 parts of dimethylphosphinous acid chloride are added at 70 to 80 ° C. under a nitrogen atmosphere to a solution of 109 parts of 3-aminophenol in 500 parts of chlorobenzene. The resulting suspension of dimethylphosphinous acid - 3 - aminophenyl ester hydrochloride is stirred for 30 minutes at 90 to 100 ° C. and then saturated with dry ammonia gas. The NH4CI formed is filtered off with suction from the solution while cold.

When the filtrate is evaporated, 161 parts (95 ° / 0) of the above are obtained Ester in the form of a yellow, non-distillable ole.

Analysis: (MW 169) Calculated ... C 56.8, H 7.1, N 8.3, P 18.3; found ... C 56.9, H 7.1, N 8.0, P 18.8.

Example 10 representation of 9 parts of 1,3-diamino-2-hydroxypropane are dissolved in 50 parts of methylene chloride. At 10 ° C., 15.7 parts of phosphorous acid diethyl ester chloride are added to this solution while cooling. The resulting suspension of the ester hydrochloride is stirred for 30 minutes at 0 ° C. and then mixed with 10 parts of dry ammonia gas. The resulting NH4CI is suctioned off at 0 ° C. The clear, colorless filtrate is evaporated in vacuo. 16 parts of the above diamine remain in the residue in the form of a colorless oil which is somewhat cloudy due to a low content of NH4Cl.

Analysis: (MG 210) Calculated. . C 40.0, H 9.1, N 13.3, P 14.8; found ... C 39.7, H 9.0, N 13.8, P 14.5.

Example 11 Representation of A mixture of 17.6 parts of monoallyl phosphorous acid bis (dimethylamide) and 20.2 parts of N-allylethanolamine is gradually heated to 90 to 1000 ° C. while stirring and passing nitrogen through, with dimethylamine being split off in gaseous form. The elimination of the dimethylamine is completed at 100 to 10 ° C. To remove volatile constituents, the resulting colorless DI is then briefly heated to 1000 ° C. in a water-jet vacuum. Yield: 28.5 parts; Colorless UI Analysis: (MW 288) Calculated ... C 54.2, H 8.7, N 9.7, P 10.7; found .. C 54.1, H 8.5, N 9.9, P 10.9.

Example 12 representation of A mixture of 93 parts of triphenylphosphile and 99 parts of 3-aminophenol is heated in the presence of a catalytic amount of sodium methylate with stirring to 160 ° C. under a vacuum of 15 mm. The phenol which distills off is collected in a receiver. The transesterification is complete after about 5 hours. 115 parts of tris (m-aminophenyl) phosphite remain in the residue in the form of a brownish ole (n2D = 1.6448), which crystallizes after prolonged standing. M.p. 110 ° C.

Example 13 Representation of A mixture of 29.6 parts of ethylphosphonous acid bis (dimethylamide) and 43.6 parts of 3-aminophenol is heated with stirring. A clear solution forms at 60 to 70 ° C., from which dimethylamine vigorously escapes at 900 ° C. The temperature is gradually increased to 1200 ° C. over the course of 4 hours.

After the elimination of dimethylamine has ended, the residue is obtained 56 parts of the above compound in the form of a reddish clear ule (n = = 1.6050).

Example 14 Representation of A solution of 43.6 parts of 3-aminophenol in 44 parts of ethyl phosphate bis (diethylamide) is heated to 100 ° C. with stirring. Diethylamine is formed, which is removed from the reaction mixture via a distillation bridge. In the course of 2 hours, 28 parts of diethylamine are split off, whereupon the reaction slowly comes to a standstill. 59 parts of the above compound are obtained as the distillation residue in the form of a clear, brown ole (II20C = 1.5983).

Claims (1)

Claim: Process for the production of new basic esters the phosphorous, phosphonous or phosphinous acid of general Formula (Z) rnP [O - R (NHR1) n] p where R is an inert aliphatic or inert aromatic Radical and Rl is hydrogen, an alkyl or an alkenyl radical, Z for one inert organic radical which is bonded to phosphorus directly or via oxygen is, m is a number from 0 to 2, ii is a number from 1 to 2 and p is a number from 1 to 3 means d a d u r c h marked that one Phosphorig-, Phosphonig- or Phosphinous acid chlorides, esters or amides with corresponding amino alcohols or aromatic hydroxyamines whose amino groups still have at least one reactive Containing hydrogen atom, converts.