SU1668363A1 - Method for synthesis of 4-oxatricyclo[4 - Google Patents

Abstract

The invention relates to heterocyclic substances, in particular the preparation of 4-oxatricyclo [4, 2, 1, 0, ^3.7 ] nonane monomer for the synthesis of polyurethane fibers. The goal is to increase the yield of the target product. To this isomerization is carried out 2 - oksimetilbitsiklo [2, 2, 1] heptene-5 in the presence of a catalyst - γ -AL ₂ O ₃ at 120 - 220 ° C and space velocity of feeding the starting material of 0.25 - 2 h ^{1 *} 99- . These conditions increase the yield of the target product to 99.9% with a purity of 99.5% against 53–63% in the known case. 1 tab.

Description

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(21) 4730511/04 (22) 08.16.89 (46) 07.08.91. Bü №29 (72) V.M.Smagin, B.S. Strelchik, S.A.Kamneva, N.G.Loginova, S.N.Ananyev, V.S.Etlis, I.V.Romanov and V .S.Lanovets (53) 547.722.07 (088.8)

(56) Henbest H.B. et all. Aspescts of stereochemistry. Part XII. A. Speslflc Directing Effectin the Mercuratlon of Some 4- Substltuted Cycbohenes and els- Hex-3-enol; J.Chem. Soc.1959, p. 227. US patent number 2440 220, cl. 549-459, publ. 1945.

(54) METHOD OF OBTAINING 4-OXATRIKOLO 4,2,1,03Jj-HOHAHA (57) . The goal is to increase the yield of the target product. For this, isomerization of 2-hydroxymethyl-bicyclo 2,2.1-heptena-5 is carried out in the presence of a catalyst, γ-A12 Oz, at 120-220 ° C and a bulk feed rate of the starting product of 0.25-2. These conditions increase the yield of the target product to 99.9% with a purity of 99.5% against 53-63% in the known case. 1 tab.

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The invention relates to an improved process for the preparation of 4-oxatricyclo 4,2,1,037-nonane, which can be used as a monomer for the synthesis of polyurethane fibers.

The purpose of the invention is to increase the yield of the target product due to the use of catalyst as a catalyst and carrying out the process at 120-220 ° C and a bulk feed rate of the starting product of 0.25-2 hours.

EXAMPLE 1 A 2-hydroxymethyl bicyclo 2.2 was passed through a glass reactor into which 10 ml (6 g) was charged at a rate of 15 ml / h for 2 hours at T 195-200 ° C. heptene-5. The result is 29.5 g of a white crystalline product with mp. 104-108 ° C.

According to gas chromatographic analysis, sample II conversion was 99.1 mol.%, Sample I 99.8 mol.%. The purity of the target product is 98.9%. After 10 work cycles

catalyst is not marked by a drop in its activity.

The PMR (100 MHz) and NMR13C (25.1 MHz) spectra of sample 1 were removed on a Tesla BS-567 A, PMR-15% solution in CCL. NMR13S-30% solution in the SMS, D20 stabilization in the capillary. Internal standard - HMDS. PMR spectrum 1 (bpm) 0.95-1.1 m (2H, H9-endo, H2-endo); 1.15-1.55 m (2H, H8-synanti); 1.59 (1H, H9-3K30, Ji 7-5 Hz, J2 13.0 Hz); 1.91 m (1H, H9-exo, Ji 10.5 Hz, and II 12, OHz, 4, OHz, 3 , OHz); 2.07m. (1N.N1); 2.26 m. (14, H6, Ji 2 Hz, J2 4.0 Hz, J3 4.3 Hz, J “10.5 Hz); 2.55.d.d. (1H. H7, Ji 5 Hz, J2 5 Hz, Ja 1.5 Hz) 3.53 U.D. (J 8 Hz) and 3.68 d.d. (Ji 4.0 Hz, J2 8 Hz), AV system 2H, CH2-0; 4.21 d.d. (1H, H3, Ji 5.0 Hz, J2 7.5 Hz).

Analysis of the C 1 NMR spectrum showed that the compound contains eight carbon atoms, two of which are combined with acid

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by the beard. By the off-resonance method, it was established that the compound includes 4-CH and 4-CH2-groups.

NMR13C spectrum (5 ppm): 32.2 d (1, C1); 36 t. (1C1, C8 or C9); 36.3 t. (1C, Cz or MF); 36.5 days (1Ј 38.7 t. (1 C, C2), 44.4 days (1 C, C7), 71.5 tons (1C, C5); 76.9 (1 C.C3 ).

IR spectra were recorded on a Specord IR instrument - 75% solution in SST); IR spectrum 1V, cm 1: 1040.1075, 1120, 1140-furan ring; 2930-CH2-0. Other examples illustrating the proposed method are shown in the table.

When carrying out the process at a temperature above 240 ° C and a bulk alcohol feed rate of less than 0.25, side retrodiene decomposition of the starting compound occurs at a temperature of less than 120 ° C and the bulk alcohol feed rate of more than 2 drops the yield of the target product.

The proposed method is more efficient than the known one, since it allows to increase the yield of the target product from 50-63 to 98.9-99.9 mol.%, While the conversion of the starting compound is 96.8-100%. High feed conversion and pro selectivity

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The process allows to obtain the target product 1 with a purity of 98.5 - 99.5% without an additional stage of purification and isolation. No wastewater is generated during the isomerization process. The operating time of the heterogeneous catalyst 7Al3g, which ensures high degrees of conversion of the starting alcohol (98.8-100%) and selectivity of the process (98.9-99.9%), is, depending on the reaction conditions, 2-5 hours, after which it can be repeatedly regenerated with a nitrogen-air mixture at 400–450 ° C for 2–3 h, and reused in the isomerization process of 2-hydroxybicyclo 2.2.1 heptene-5.

Claims (1)

The starting compound can be synthesized by the reaction of diene synthesis from cyclopentadiene or its dimer-dicyclopentadiene and allyl alcohol. The invention of the method for producing 4-oxatricyclo 4.2.1.0 g of nonane by isomerization of 2-hydroxymethylbicyclo (2.2.1) heptene-5 in the presence of a catalyst with heating, in order to increase the yield of the target product, As a catalyst, it is used in ANYEZ and the process is carried out at 120-220 ° C and a bulk flow rate of the starting product of 0.25-2 h -one