The method of obtaining alpha-adamantylidene aldehydes

 

(57) Abstract:

The invention relates to the chemistry of adamantane derivatives, and in particular to a new method of obtaining-adamantylidene aldehydes of General formula

where R1=H, R2=CH3WITH3H7WITH4H9; R1=R2=CH3,which are intermediates for the synthesis of biologically active substances, using the adamantane derivative. The method consists in joining the adamantane derivative of the corresponding aldehyde, and as adamantane derivative use 1,3-dehydroalanine, and as aldehyde: propanal, pentanal, hexanal, Isobutanol, and the process is carried out at a molar ratio of 1,3-dehydroalanine and the aldehyde of 1:4-6, in the environment of the original aldehyde at a temperature of 35-40°C. for 3-5 hours. The method allows us to simplify the process of obtaining, as well as to obtain the target compounds branched structure.

The invention relates to the chemistry of adamantane derivatives, and in particular to a new method of obtaining-adamantylidene aldehydes of General formula:

which are intermediates for the synthesis of biologically active substances.

The disadvantage of this method is, first of all, the difficulty of obtaining the original N-tert-butylaminoethyl-1 aziridine, as well as the absence of the possibility of synthesis of other adamantylidene aldehydes.

Another way to obtain atlanticchallenge.ca is blowing carbon monoxide cooled to 0°With a mixture of adamantane, methylene chloride and aluminium chloride. The output of atlanticchallenge.ca 49% [and.with.1793313 THE USSR, MKI 3 07 WITH 47/44. A method of producing substituted-1-aldehyde / Y. Y. Polis, B. P. Raugel, E. E. liepiņš. - Publ. in B. I., 1977, No. 5].

The disadvantages of this method are: the complexity and multi-stage selection of the target product, the technological complexity of the process and low yield of the target product.

The most common ways of obtaining adamantylidene aldehydes are the oxidation of the corresponding alcohols leads to compounds, which lead or hydrolysis of the corresponding diacetate obtained by the interaction ortogonalnogo ether and the corresponding Grignard reagents. The output of both methods is approximately the same and is 37-57% [Stepanov, F. N., Dougan N. L. Aldehydes number of adamantane// Zhur.org.chem.. - 1968. - So 4. -target compounds (in terms of original adamantane, including the stage of synthesis of the starting compounds, the yield of the target products does not exceed 12%), complexity, and low adaptability of individual stages, particularly stage magyarkanizsa synthesis dangerous fire and placed high demands on the purity of the reagents.

Closest to the proposed invention is a method in which 1-adamantylamine obtained from the functional derivative of adamantane, characterized in that the functional derivative use nitrile 1-adamantanecarbonyl acid, which restores the product of the interaction of chloride tin (II) chloride with hydrogen in the presence of diethyl ether obtaining hexachloropropane salt 1-adamantylamine, which is treated with excess of water to obtain 1-adamantylamine at a molar ratio of nitrile adamantanecarbonyl acid to tin chloride and diethyl ether equal 1:1,5-2:6,2:7 [Pat.2163591 RF, MKI 7 07 47/34, 45/44/2001].

The disadvantages of this method is that for this reaction needs a catalyst of tin chloride (II), is used diethyl ether - dangerous fire, bicarbonates acid is a complex and multistage.

A common shortcoming of all these methods is that by using them it is possible to synthesize adamantylidene aldehydes having only a linear structure.

The task of the invention is to develop technological molestating method of synthesis adamantylidene aldehydes, including branched structures, proceeding with a high output.

The technical result is a simplification of the production method, as well as the opportunity to obtain the target compounds branched structure.

The technical result is achieved in a new method of obtaining-adamantylidene aldehydes of General formula:

which consists in joining the adamantane derivative of the corresponding aldehyde, and as adamantane derivative use 1,3-dehydroalanine, and as aldehyde - propanal, pentanal, hexanal, Isobutanol, and the process is carried out at a molar ratio of 1,3-dehydroalanine and the aldehyde of 1:4-6, in the environment of the original aldehyde at a temperature of 35 to 40°C for 3-5 hours.

The essence of the method is the reaction of joining 1,3-dehydroalanine aldehydes in plucky attach data aldehydes in high yields in a fairly mild conditions in one stage.

It should be noted that the aldehydes are reactions involving the carbonyl group and not a typical reaction in which the aldehyde reacts for the C-H-carbon atom.

The advantage of this method is the high output (60-78%), as well as the possibility of obtaining almost any homologues of this series, which are also intermediates for the synthesis of biologically active substances.

As studies have shown, the selectivity of the reaction is very sensitive to temperature. It was found that when the reaction temperature from 35 to 40°With the yield of the target products is 60-78%. Further increase in temperature (up to 65°C) leads to a decrease of the yield of target products to 42%, which is apparently connected with the course side of the aldol condensation. The presence of by-products of aldol condensation source and adamantylidene aldehydes confirmed by mass spectroscopy. Lowering the temperature below 35°C leads to a decrease of the yield of the target products.

The optimal molar ratio of reagents 1,3-DCA: aldehyde is 1:4-6. If the ratio of 1,3-DCA: aldehyde of 1:2 along with the target reaction product was separated unreacted 1,3-digid the The optimal duration of response 3-5 hours ceteris paribus. Further increase in the duration of the reaction does not significantly change the yield of the target product. Decreasing the duration of the reaction to 1-2 hours the yield of the target product is reduced by 20-30%.

The reaction is performed in the environment of the original aldehyde, which greatly simplifies the process. Conducting the reaction in a nonpolar environment or monopolarly solvents such as hexane and diethyl ether, reduces the yield of the target product to 0-5%. The use of more polar solvents is unacceptable in view of the high reactivity of 1,3-DHA, which reacts with the solvent.

The method is as follows.

To 4-6 fold molar excess of aldehyde is poured a solution of 1,3-dehydroalanine in the same aldehyde. A mixture of 1,3-dehydroalanine and aldehyde are heated for 3-5 hours at a temperature of 35 to 40°C, after which the aldehyde is distilled off. The regenerated aldehyde does not contain any impurities and is suitable for reuse in the same synthesis. Thus, in the industry you can organize recycling the aldehyde with the addition of the calculated amount of fresh reagent. Synthesized-adamantyl who is in 60-78%.

The structure of the target product is confirmed by IR spectroscopy, elemental analysis and qualitative reaction to the presence of carbonyl group - interaction-adamantylidene aldehydes with dinitrophenylhydrazine. This interaction was conducted immediately after the selection adamantylidene aldehydes from the reaction of adamantylamine 1,3-dehydroalanine. The interaction was carried out in an ethanol medium, in the presence of acid catalyst at a molar ratio of aldehyde: dinitrophenylhydrazine 1:1,2, at room temperature, and within 15-20 minutes led to the target compounds with the release of 84-98%. The high speed of this interaction leads to the conclusion that adamantly radical practically does not reduce the reactivity of aldehydes in the reaction of condensation by a carbonyl group. Upon completion of the reaction, the target product was filtered and precrystallization from aqueous alcohol.

The invention is illustrated by the following examples:

Example 1. Synthesis of 2-(1-substituted)-propanal.

In a reactor with a stirrer to 9 g (0.15 mol) of propanal in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 4 g (0.03 mol) fresh is Argonaut, then bring the temperature of the reaction mass to 35 to 40°C, incubated with stirring for 3 hours until the disappearance of the insoluble aldehyde 1,3-DCA.

Upon completion of the reaction the excess aldehyde is removed by distillation, the residue is vacuum to remove unreacted 1,3-DCA, after which the product is distilled (BP.=137-138/4 mm RT. Art.) and obtain 4.6 g (0,023 mol, 60%) 2-(1-substituted)-propanal representing white transparent liquid with aldehyde odor, nD=1,5104.

Found, %: C 81,32; N 10,55; 8,13

C13H20ABOUT

Calculated, %: 81,20; N 10,48; 8,32

The infrared spectrum , cm-1: 2890, 2848, 1720, 1450, 1417, 1352, 1064, 1028

Synthesis of 2-(1-substituted)-propanol-N-(2,4-dinitrophenyl)-hydrazone.

To 2.4 g (0.012 mol) of dinitrophenylhydrazine add 10 ml of concentrated sulfuric acid, then with stirring, 15 ml of water. In the warm solution is poured 30 ml of alcohol and with stirring was added a solution of 2 g (0.01 mol) of 2-(1-substituted)-propanal in 5 ml of alcohol. Maintain the reaction mass for 15 minutes at room temperature, the precipitated crystals are filtered and recrystallized from isopropanol. Obtain 3.4 g (0,0087 mol, 84,2%) of 2-(1-substituted)-propanol-N-(2,4-dinitro is.d: 0.95-0.97 m (3H, CH3); 1.68 s, 2.0 s (Ad, 15H); 2.0-2.1 m (1H, CH); 7.92, 8.2, 8.85 (3H, Ph), 8.59 (1H, CH=N); 11.35 (1H, NH);

Mass spectrum, m/e): 372 (1%)% M+, 135 (14,3%) Ad+, 41 (100%) [P3H5]+

Found, %: C 61,31; N 6,56; N 15,12; O 17,01

C19H24N4O4

Calculated, %: C 61,28; N 6,50; N 15,04; O 17,18

Example 2. Synthesis of 2-methyl-2-(1-substituted)-propanal.

Similarly, from 13 g (0.18 mol) of Isobutanol and 4 g (0.03 mol) svezheosazhdennoi 1,3-DCA obtain 4.6 g (0,022 mol, 76%) of 2-methyl-2-(1-substituted)-propanal representing a colorless transparent liquid, nD=1,5185, BP.=121-123/4 mm RT.article.

Found, %: C 81,65; N 10,92; 7,43

C14H22O

Calculated, %: C 81,50; N 10,75; 7,75

The infrared spectrum , cm-1: 2892, 2846, 1718, 1452, 1420, 1351, 1062, 1026

Synthesis of 2-methyl-2-(1-substituted)-propanol-N-(2,4-dinitrophenyl) hydrazone.

Similarly, from 2.3 g (to 0.011 mol) of dinitrophenylhydrazine and 2 g (0,0097 mol) of 2-methyl-2-(1-substituted)propanal obtain 3.8 g (0,0094 mol, 96,2%) of 2-methyl-2-(1-substituted)-propanol-N-(2,4-dinitrophenyl) hydrazone, representing a yellow crystalline material, MP.=250-251°C.

PMR-spectrum (M. D.: 1.1 (6N, 2CH3); 1.7, 1.99 with in Ad, 15H); 7.9, 8.1, 8.8 (3+

Found, %: C 62,22; N 6,86; N Of 14.57; O 16,35

C20H26N4O4

Calculated, %: C 62,16; N Is 6.78; N 14,50; O 16,56

Example 3.

Synthesis of 2-(1-substituted)-pentanal.

Similarly, 10 g (0.12 mol) of Pentanes and 4 g (0.03 mol) svezheosazhdennoi 1,3-DCA maintained at a temperature of 35 to 40°C for 5 hours and get 5 g (0.22 mol, 75,6%) of 2-(1-substituted)-pentanal representing a colorless transparent liquid, nD1,5150, BP.=141-143 /3 mm RT.article.

Found, %: C 81,90; N 11,04; About 7,06

C15H24O

Calculated, %: C 81,76; N 10,98; 7,26

The infrared spectrum , cm-1: 2886, 2840, 1715, 1450, 1417, 1350, 1061, 1021

Synthesis of 2-(1-substituted)-pentanal-N-(2,4-dinitrophenyl) hydrazone.

Similarly, from 2.2 g (to 0.011 mol) of dinitrophenylhydrazine and 2 g (0,009 mol) of 2-(1-substituted)-hexanal obtain 3.5 g (0,0084 mol, of 92.7%) of 2-(1-substituted)-pentanal-N-(2,4-dinitrophenyl) hydrazone, representing a yellow crystalline material, MP.=97-98°C.

PMR-spectrum memorial plaques: 0.91-0.94 m (3H, CH3); 1.45-1.49 m (4H, CH2); 1.59 s, 1.97 (Ad, 15 NM); 1.98-2.0 m (1H, CH); 7.9, 8.25, 9.0 (3H, Ph); 7.94 (1H, CH=N); 11.12 c (1H, NH);

Mass spectrum, m/e): 400 (2,2%) M+, 135 (22%) Ad+, 41 (100%) [C3H

C2lH28N4O4

Calculated, %: C 62,98; N 7,05; N 13,52; O 16,45

Example 4.

Synthesis of 2-(1-substituted)-hexanal.

Similarly, from 12 g (0.12 mol) of hexanal and 4 g (0.03 mol) svezheosazhdennoi 1,3-DCA obtain 5.5 g (0,023 mol, 78,1%) of 2-(1-substituted)-hexanal representing a colorless transparent liquid, nD=1,5216, BP.=151-154 /3 mm RT.article.

Found, %: C 82,06; N. Of 11.26; 6,68

WITH16H26ABOUT

Calculated, %: C 81,99; N 11,18; 6,83

The infrared spectrum , cm-1: 2884, 2842, 1715, 1451, 1412, 1348, 1058, 1020

Synthesis of 2-(1-substituted)-hexanal-N-(2,4-dinitrophenyl) hydrazone.

Similarly, from 2 g (0.01 mol) of dinitrophenylhydrazine and 2 g (0,0085 mol) of 2-(1-substituted)-hexanal obtain 3.6 g (0,0083 mol, 98,1%) of 2-(1-substituted)-hexanal-N-(2,4-dinitrophenyl) hydrazone, representing a yellow crystalline material, MP.=167-168°C.

PMR-spectrum memorial plaques: 0.85-0.9 m (3H, CH3); 1.39-1.42 (6N, CH2);1.55, 1.95 (Ad, 15 NM); 1.97-1.99 m (1H, CH); 7.6 (1H, CH=N); 7.8, 8.24, 9.0 (3H, Ph); 11.0 c (1H, NH);

Mass spectrum, m/e): 414 (8%) M+, 135 (100%) Ad+, 41(18%) [C3H5]+

Found, %: C 63,82; N 7,33; N 14,06; 14,79

C22H30N4O41N and mass spectra.

Way to obtain-adamantylidene aldehydes of General formula

where R1=H;

R2=CH3WITH3H7WITH4H9;

R1=R2=CH3,

using the adamantane derivative, characterized in that the method consists in joining the adamantane derivative of the corresponding aldehyde, and as adamantane derivative use 1,3-dehydroalanine, and as aldehyde: propanal, pentanal, hexanal, Isobutanol, and the process is carried out at a molar ratio of 1,3-dehydroalanine and the aldehyde of 1:4-6, in the environment of the original aldehyde at a temperature of 35-40°C. for 3-5 hours



 

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