SU509240A3 - The method of obtaining-oxibenzyl-phosphonates - Google Patents

Description

(54) METHOD FOR OBTAINING PGOSE BENZYL PHOSPHONATES

NaOCa Hj, MgiOCj HS) 2. Compounds of diesters of phosphonic acid with alkali metals can also be used as bases.

Preferably, lithium amide or a sodium derivative of the corresponding phosphorous diester is used as the base.

According to the proposed method, it is advantageous to use the starting reagents. equimolar ratio. If necessary, one of the two components can be used in excess of up to 20%.

Usually the process is carried out in the presence of 1-30 mol. % base, preferably 5-10 mol.%,,

The reaction is preferably carried out in nitrogen or in an inert gas at normal or reduced pressure, for example, 10-100 mm. The reaction can be carried out, for example, in such a way that the starting reagents and the base without solvent are heated under reduced pressure until the release of the amine is complete, or in such a way that the base is first added to the phosphoric acid diester solution and then increased in telorate Ribavl solution of p-hydroxybenzyl dialkylamine in the same solvent.

EXAMPLE 1 To 0.99 g (0.03 mol) of metashic sodium was added to 13.8 g (0.1 mol) of dystilphosphite with 100 ml of toluene. During the dissolution of the sodium, the temperature rises to 40 ° C. 26.3 g (0.1 mol) of (4-hydroxn-3,5-ditert-butylbenzene 1) -dimethylamine in 150 ml of toluene are added to the Crasteor. The mixture is then refluxed for 1 hour with dimethylamine gas. At the end of the allocation of dimethylamine smgs

cooled and water was added thereto. The toluene phase is washed to neutrality and evaporated. The residue is recrystallized from ligroin. 26.8 g (75%) of 4-hydroxy-3 da-Tpei diethyl ester are obtained. bottles of lbeizdaphosphon

acids; T. 101.122.C

If, in this example, replacing dimethyl phosphate of equimolecules with a quantity of phosphoric acid diester, observing the same mode of operation, the physical properties and yield close to the indicated diesters of 4-hydroxy-3, 5-ditert-butylbenzylphosphonic TbJ are given in tab. one.

Table 1

(sns0) 2to

(С4Н90) 2РНО

(Cl2H250) 2PHO

SNS - (CgHi, -C-CH20) jPHO

SNS

(CH2 CH-CH20) 2PHO (CICH2 CH2O) 2PHO

EXAMPLE 2 13.8 g (0.1 mol) of diethylphosphite and 29.1 g (0.1 mol) of (4-hydroxy-3,5-di-tert-butylbenzyl) - diethylamine are heated to 80 ° C, pass through a mixture of weak nitrogen. After adding 0.1 g (0.0044 mol) of lithium amide, the pressure is set to 15 Torr using a C1 water jet pump and the mixture is heated to 100 ° C. There is intense gas formation due to the release of dithyl fl to the mixture. fepe3 an hour added 0.3 g of glacial acetic acid and 50 ml of ligroin. When cooled, 4-hydroxy-3,5-di-gre-butyl 15-methyl ethyl ester is formed.

180-184 / 0,2

45- 48

Light yellow oil

Light yellow oil

160-165 / 0.1

113-1G7

benzylphosphonic acid as white crystals; t. Sh1. 122 ° C, yield 32 g (90%).

By replacing (4-hydroxy-3,5-di-butylbenzyl) - dystilamine in this example with an equimolecular amount (3-tert-butyl-4-hydroxy-5-methylbenzyl) - dietklamine, it is obtained with a similar mode of operation and using different dialkylphosphites The dialkyl esters of (3-treg-butyL4-hydroxy-5-methylbenzyl) -phosphonic acid listed in Table 2 are in good yield. 2

(CHjO) 2PHO (CjH50), PHO

(C4H9-CH-CHiO) 2PHO

(C8Hz70) 2gо

P p and M ep 3. 29, 3 g (0.05 mol) of dioctadecyl phosphite and 13.3 p (0.05 mol) (4-hydroxy-3,5-d-tert-butylbenzyl) -dimethylamine are heated to 60 ° C, pass through the mixture a weak stream of nitrogen. This forms a homogeneous melt. Add 0.3 g (0.013 mol) of lithium amide; with the help of a single-jet pump, the pressure is reduced to 15 torr and the mixture is slowly heated to 100 ° C. The formation of diethitamin begins at 80 ° C. After an hour, the mixture is cooled to 50 ° C and added to 1.0 g of glacial acetic acid. The melt disappears when cooled (C1bN3ZO) aRNO

С (22Н450) 2РНО

(CijHzs -S-CH2CHjO) araO (CisHsT -S-CH2CH20) aPHO

P p and m e p 4. 23.4 g (0.1 mol) of diphenylphosphite are dissolved in 50 ml of absolute toluene. The solution is cooled to 5 ° C and 0.48 g (0.02 mol) of sodium hydride is added to it. The mixture is heated to boiling and a solution of 26.3 g (0.1 mol) of (4-shdroxy-3,5-di-tert-butyl) dimethylamine in 100 ml of absolute toluene is added dropwise to it. The mixture is then boiled until the release of dimethylamine is stopped (about 4 hours). After cooling, the mixture is neutralized with a small amount of glacial acetic acid and water is added to it. Toluene of the 15th phase is washed to neutral and evaporated. The residue is recrystallized. 1. Melt from hexane. Obtain 33 g (73%) of diphenyl ether (Phy / hroxy-G 3-da-tert-butylbenzyl) - phosphonic KHCJioibj; t. .

102

102

216/5

69-71

Scientific research institute to room temperature. After recrystallization from acetone, 35 g (90%) of dioctadecyl ester (4-hydrox-3,5-di-tert-butylbenzyl) -phosphonic acid are obtained; t. Sh1. 57 ° C.

Replacing dioctadeciphosphite in this example with an equimolar amount of phosphorous acid diester, with a similar cutting, we obtain disphirs (4-hydroxy-3,5-di-tert-butylbenzyl) -phosphonic acid with yields above 85% and melting points indicated in Table . 3,

Table 3

46-48

Liquid

50

Replacing in this example diphenylphosphite with equimolecules with a quantity of di- (tert-octylphenyl) phosphite, is obtained with the same mode of operation after distilling off the solvent with a good yield of di-tert-octylphenyl ether (4-hydroxy-3,5-datretbutylbenzyl) phosphonol acid in the form of glass with a light yellow color.

PRI me R 5. 13.8 g (0.1 mol) of diztilfosfita and 17.9 g (0.1 mol) of (4-hydroxy-3,5-dimethylbenzyl) -dimethylamine; heated to 100 ° C. At this temperature, 0.4 g (0.01 mol) of sodium methylase is added, then the pressure is reduced to 15 Torr. After termination of the reaction, which takes about 1 hour, the mixture is cooled and neutralized with glacial acetic acid. The melt is digested with hexane,

and crystallization occurs. After the cross-over of the test, the hexash get a diet (4 - gdfoks -3,5 dimethylbenzyl) -phosphonic acid diet in 80% yield; t, pl. 72 ° C.

Replacing in this apoMsfe (4-hydroxy-3,5-dimethyl-benzyl) -membrane mia with an equimolecular co-property (Fischkmso-3,5-diisopropylben) -dimeoimine, is obtained with a similar quality of diethyl ether (4-hydroxy-I) , 5-diisopropylbenzyl) -phosphonic acid with a yield of 65% liquid with m.p. 163 S / O, 15 "and.

PRI me R 6. 3.8 g (0.1 mol) of diephosphite diet and 30.5 g of N- (4-hydroxy-3,5-di-tert-butylbenzyl) morpholine (m. 93- 94 C) are not mature in the presence of nitrogen to 1QD ° C. After the addition of 0.2 g (0.005 mas of sodium amide using a water jet pump, the pressure is reduced to 15 Torr and the mixture is kept for 2 hours at 106 ° C. When the reaction is stopped, the mixture is cooled and neutralized with a small amount of glacial acetic acid. When processing the reaction mixture warm ligroin is released to {methyl diethyl ether (4-hydroxy-3,5-d-t-butnl-benzyl) -phosphonic acid.

Yield 28 g (80%), mp, after recrystallization of sym from luroin 122 ° C.,

Claims (4)

Claims 1. Method for preparing p-hydroxybenzylphosphonates of the general formula R V -Or-k About -f -SN G  -ABOUT where RI and RJ are straight or branched chain alkyl, cycloalkyl, aralkyl; RS and R4 - independently of each other alkyl with straight or branched chain, cycloalkyl, alkylthioalkyl, alkyloxalkyl, haloalkyl, alkenyl, phenyl, alkylphenyl or together - the -CH2CH, or -O groups In order to simplify the process, the corresponding l-oxnbenzyl dialkylamine is reacted with phosphorous diester in the presence of a base with heated 2. The method according to p, 1, about t l and h a y i and with the fact that the process is carried out at 60-120 ° C., 3. The method according to claim 1, 1 and 2, and with such that lithium amide or sodium derivative of the corresponding phosphoric acid diester. 4. An osuob according to claim 1, characterized in that the process is carried out in the presence of 1 to 30 mol% of a base.