SU770012A1 - D,1- or 1-n-methacryloyltryptophan as monomer for producing polymers with covalent-attached tryptophan groups - Google Patents

Description

a luminescent label (ML) of another value, for example (antr of prices containing). Data from this study is necessary for the study of the proteins of the itecbMa non-proliferative and extensively 13: the present time MeroaoiM PL.

This monomer is obtained by; in; 1aimine methacrylo, ilchloride with d, l- or IN-TpiHinTo aHOM s in an aqueous-alkaline medium pH 9-10 and a temperature of 0 ° C. The resulting product is isolated in the form of dicyclohexl M1MONIUM salt with further isolation from salt using an ion exchange resin.

The structure of the obtained d, l-, or 1-M-methacryloyltryptophs was confirmed by elemental a-analysis, IR- and UV-oectography, measurements of specific rotation.

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Example 1. Getting d, l, N-imetacryloyltrypto. Faia. 1.94 g (0.009 mol) of d, l-tryptophan is dissolved with stirring in 2 ml of a 20% aqueous solution of NaOH and 8 ml of water and 1.5 Mir Cu2Cl5 are added. When cooled with ice and intensively; M shermeshivaii were added dropwise 2.9 ml (0.03 mol) of methacry | I.loilchlor "yes, in which there was 2.5 mt b" "(naphthas" but: HI) - / g-PheN: Ilendiami: on, the pH of the solution during the reaction is kept constant (pM 9-10) by adding a 20% aqueous solution of NaOH. After adding the total methacrylonl chloride, the reaction is continued for another 30 minutes under ice cooling and 3 hours at room temperature. The reaction mixture is then neutralized by adding a 20% aqueous solution of hydrochloric acid. Dropped out; the precipitate is washed with water and dissolved in chloroform. The solution is dried over MgSO, and the solvent is evaporated in vacuo. 2.8 g of substance are obtained.

The crude product (2.8 g) was dissolved in a mixture of 6 ml of dioxane and 20 ml of triethyl acetate and 5.6 g of dyadiclohexylamine were added. The mixture is heated with water at 60–80 ° C 30, m: in. The precipitate formed on cooling is filtered off. The ether is washed several times with ether: pO | M, and it is formed in a vacuum. The output of dicyclohexylamine. Alumina salt d, l-N-MeTacrylo ltdaltophan 3.6 g (72% of theory). T „, 187-190 ° C.

1.5 g of dicyclohexyl. Copium salt of d, l-N-methacryloyl type boron crystallized on 7 ml of ethanol. The precipitated crystals are filtered off, washed with efflrom, and existed in a vacuum. 0.7 t of product is obtained. Т „„ 191 -192 ° С. Elemental analysis data of dicycloche, xyloxy ammonium salt d, l-N methacryloyltrnptone a.

Calculated,%: N 9.28; H 8.66, C 71.48. CrNTHeOZS Found,%: C 70.81; 70.87; N 9.31; 9.31; P 8,86; 8.76.

For the isolation of d, ln-methacryloylpiptophan dicyclohexylammonium salt

(229 mg) is dissolved in 12 ml of 50% ethyl alcohol and treated for 30 minutes with the DOWEX-50 ion-exchange resin in the H-form under static conditions. The ion exchange resin is filtered off and washed with 2 ml of 50% ethanol. The filtrate is evaporated in walsuum to a slight turbid kiHH. And the crystal is led from the bottom while cooling to -10 ° C. The crystals are separated, washed, water, dried in vacuum. Yield (43% of theory). TP, 115-116 ° C.

Dalsch elemental analysis of d, lnn-MeTacrnlonlltripgofana.

Calculated,%: C 66.15; H 5.92; N 10.29.

CisHisOgNa.

Found,%: C 66.26; 66.31; H 5.96; 6.19; N 10.28; 10.31.

In the infrared d, ln-mectacry, triptophia, there are absorption bands,

3410 (NH stretching vibrations of indole rings), 3320 (NH oscillations of a.midine), 1780 (C O in COOH), 1643: And 1600 (C C and amide I band), 1530 (amide II), 1230 (valent fluctuations from 0 to

COOH), 760 (nonplanar deformation oscillations of the benzene ring in an indi- nal fitting).

Example 2. Synthesis of 1-M-metacr1Ilayltryptophan.

Synthesis of the product; w / d s conditions of the VI of Example 1. From 1.94 tons of the T-porttode (specific rotation:; Tananol — 30 ° C), 2.8 g of the crude desired product are obtained.

For the preparation of the d-cyclohexyl 1 ammonium salt of l-N-methacid.il-O.Il-type boron, the crude product (2.8 g) is dissolved in 7 ml of dioxane. To the filtrate were added 9 ml of ethyl acetate and 6 ml of d.cyclohexylamine. The mixture is heated in a water bath at C for 30 minutes. The crystalline precipitate formed during the cooling of the mixture was separated, washed with ether, and dried in vacuo. 2.88 g of salt is obtained (66% of theory). Mp 183-

186 ° s. Salt is crystallized from 10 ml of ethanol. 1.2 g of the di.cyclohexyl ammonium salt of 1-Y-meta.cryloyltri1ptophan are obtained. Mp 189-191 ° C. Da.n1nye elemental analysis of dicyclohexylammonium salt:

Calculated,%: C 71.48; H 8.66; N 9.28. CrnHeOzMz.

Found,%: C 71.85; 71.92; H 8.66; 8.89; N 9.48; 9.36.

In order to isolate lN-methacryloyltryptophan, 553 mg of 1-M-di-chloteloxylammonium salt: meta, kryloyl-crypt-topo, ana are dissolved in 20 ml of 50% ethanol and O | scavenge with DAUEX-50 IB H-form ion exchange resin for 30 mi .and.

The resin is filtered off and washed with 10 ml of 50% ethanol. The washing liquid is combined with the main plant, m and evaporated in a vacuum to a cloudy l. Crystallization is carried out at -10 ° C.

the crystals are separated, washed with water, su

Claims (1)

Claims d, l- or lN-methacryloyl tryptophan, formula cn ₃ coon cn ₂ -c-co-in-cn-cn ₂ as a monomer for the preparation of polymers with covalently attached tryptanes and groups. Source of information taken into account during the examination: 1. Uernura, Takahiko et all, 'The synthesis and asymmetric adsorption of optically active resins sbarting from varions a-aminoacids, Nippon Kagaku Lasshi, 88 (11), 1238-9, 1967.