JPS588368B2 - 4-Homoisotwistane-EXO-2- - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel compound, 4-homoisotwistane-exo-2-ol (exo-2-hydroxyl link [5.3.1.03.8] undecane). This relates to the manufacturing method of (■).

Specifically, 4-homoisotwist-2 represented by formula (I)
-ene (new compound) is an organic boron compound R1R2BH represented by formula (II) (wherein R1 and R2 are each hydrogen and a straight-chain or branched alkyl group, preferably an alkyl group having 6 or less carbon atoms). 4-homoisotwistane-exo- 2
-Relates to a method for producing oars.

Generally, to introduce functional groups into polycyclic hydrocarbons, a reaction that proceeds via an intermediate carbocation is used, but the present inventors have developed a method for introducing functional groups into polycyclic hydrocarbons.
According to the results of detailed research on undecane, the bridgehead cation at the 3-position is the most stable, so a functional group can only be introduced at the 3-position.

The compound (■) obtained by the present invention with a functional group introduced at the 2-position is the first example to have a functional group at a position other than the 31-position, and has a basic functional group called a hydroxy group at the 21-position. It is a very important compound for synthesizing derivatives with functional groups.

The fact that the product alcohol is exo means that the hydroboration reaction generally performs cis addition closer to the exo side, where there is less steric interference, and the subsequent oxidation reaction with hydrogen peroxide maintains the steric configuration. It can be easily estimated from the facts.

This also means that 4-homoisotwistan-2-one obtained by oxidizing alcohol (II) with CrO3 is oxidized with Li.
When reduced by AlH4, an alcohol different from the original alcohol (4-homisoisostane-endo-2
- All) can be confirmed rather than being guided by.

Considering that various derivatives of adamantane, which is a similar polycyclic hydrocarbon, have various physiological effects, this compound (■) is expected to have similar physiological activities, and is also a textile oil component. , extreme pressure agents, rust preventives, lubricating oil additives, etc., and is also important as an intermediate for obtaining these useful compounds.

In carrying out the present invention, the amount of organic boron used is:
It may be used in an equivalent amount to the olefin, but if it is used in excess of about 10%, the olefin can be reacted completely.

The reaction conditions were those described by Brown et al. for hydroboration (G. Zweitel, H,C
．． Brown10rganic Reactions
1 3, (1963), organic borons (mentioned above) are replaced with diethyl ether, dibutyl ether,
4-Homointwist-2-ene is added dropwise to a solution of tetrahydrofuran, diglyme triglyme, etc. dissolved in an ether solvent. By oxidizing with hydrogen peroxide in the presence of 4-homoisotistan-exo-2-ol, the target product can be obtained.

The reaction temperature when dropping olefin is -20℃ to +
A temperature in the range of 80°C is satisfactory, but room temperature is sufficient since there is no significant change in yield.

The reaction temperature for oxidation with hydrogen peroxide in the presence of an alkali can range from -70°C to +50°C;
It is preferable to carry out cooling to a temperature in the range of 0°C to +10°C.

Examples are shown below to explain the method of the present invention in more detail.

Example 1 4-homoisotwist-2-ene 1.77 g (12 mmol), sodium borohydride 0.14? (3.7 mmol) and 5 ml of tetrahydrofuran dried over sodium metal, the reaction system was purged with nitrogen and, with stirring at room temperature, an ethereal solution of trifluoroboron with 0. H7
(4.8 mmol) and 5 ml of tetrahydrofuran was added dropwise over about 1 hour.

After the dropwise addition, stirring was continued for another hour, and then 3N was added while cooling.
-2 ml of caustic soda aqueous solution, 35% hydrogen peroxide solution 1.
Add 8ml.

After the reaction, sodium chloride is added to separate the layers, and the organic layer is extracted with ether.

After drying over anhydrous magnesium sulfate and distilling off the solvent, white crystals of 4-homoisoisostane-exo-2-
All 1.52P (yield 77%) is obtained.

Melting point 92-93°C. Elemental analysis: Analysis value C, 79.06; H, l. 0.87%C11H
Calculated value C as 18o, 79.4 6; H11 0.9 2%ir (
Liquid film cm-1): 3350 (broad, νo-H)
, 1070, 1020 (S1νo-c) pmr (CDcl3 solvent, TMS internal temperature standard δ) 3.6 (
1. H), 3.4 (LH), 2.8 (IH), 2.1 (
0 days), 2.0 to 1.0 (complex multiplet) 5ms, m/
A? (Relative intensity) 166 (M+, 19), 1. 48(
55), 135 (40), 92 (39), 91 (33)
, 81(32), 79(38), 67(37), 41(
36), 28(34), 1. 8(100) Reference Example 1 4-Homoisotwist-2-ene represented by formula I is synthesized as follows.

3-Bromo 4-Homoinosoistane 8.22F (36
mmol) 20 m of toluene dried over sodium metal
1.4 g (36 mmol) of sodium amide is added to the solution consisting of 1.1 g of sodium amide, and the mixture is stirred for 2 hours under refluxing toluene.

After the reaction is cooled and the reaction solution is fractionally distilled, colorless [5.3.1.03°8] undecene-2 (boiling point 90-
92℃/1. 9 miHg).

Yield 2.75'? (Yield 52%) Elemental analysis: Analytical value C, 88.9; H, 11.1% Calculated value as C 1 1 H6 C, 89.1; H, 10.9%2! ir (liquid film cm'): 3020 (rH-c-), 162
0 (rc=c), 1450 (CH2), 840, 820
, 810 pmr (CDcl3 solvent, TMS internal standard δ) 5.9 (
doublet), 29-0.9 (complex multiplet) ms, m/A
(Relative intensity) 1.48 (M+, 41), 1. 05(2
5), 94 (100), 9 2 (2 8), 91 (5
1), 77 (25), 66 (33), 41. (26
), 18(39) Reference Example 2 4-Homoisotwistane-endo-2-ol was synthesized as follows.

4-Homoisotwiskun-eXo-2-ol 0.7g
(4.2 mmol) of a solution consisting of 5 ml of acetone.
Cool with ice to 10°C, and add 1 part of water from the dropping funnel while stirring.
ml, concentrated sulfuric acid 0.5ml and triacid chromium 0.35? (3
．． An oxidizing reagent consisting of 18:limole) is added dropwise over about 10 minutes while maintaining the temperature.

After the dropwise addition, allow the reaction to proceed at room temperature for an additional 2 hours.

After the reaction, add sodium bisulfite aqueous solution until the reaction mixture becomes completely green in order to decompose the excess chromic acid.

The reaction solution was extracted three times with 3 oml of ethyl ether, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off. Yield: 95%).

If this product is recrystallized from n-hexane, m. p. 60
Crystals of ~61°C are obtained.

Elemental analysis: Analysis value C, 80, 52: H, 9.64% Revised value C as C11H16O, 80.44; H, 9.83% ir (Nujol, cm'): I700 (S, vc=o
), 1200, 1090 ms. 1. 64 (M+) 4-Homoisotwistan-2-one obtained here 0.
A solution consisting of 6 g (3.6 mmol) in 5 ml of dry ethyl ether was mixed with 0.1 (2.
6 mmol) was added dropwise at room temperature to a reaction system consisting of 5 ml of dry ethyl ether.

After the dropwise addition, the reaction was continued for an additional 2 hours while gently refluxing the ethyl ether.

After the reaction, it was cooled and hydrolyzed with methanol and then water, acidified by adding a hydrochloric acid solution, and 30% of ethyl ether was added.
Extract 3 times with ml.

Drying over anhydrous sodium sulfate, filtering, and distilling off the ethyl ether yields colorless crystals of 4-homoisotwistane.
0.46 g (yield 76%) of 6ndo-2-ol was obtained.

If this product is recrystallized from n-hexane, the melting point is 95-9
A pure product at 6°C is obtained.

Elemental analysis: Analysis value C, 79.21; H, 11.21% C11H, 8
Calculated value as 0 C, 79.46; H, 10.92% ir (Nujol, cm-1): 3350 (bro
ad, vo-H), 1150, 1070, 1040 ms, m/ 73166 (M+)

Claims (1)

[Scope of Claims] 1 4-Homoisotwist-2-enwo formula (1■
) (In the formula, R1 and R2 each represent hydrogen and a linear or branched alkyl group, and R1 and R2 may be combined to form an alkylene group). A method for producing 4-homoisotwicune-exo-2-ol represented by the formula (■), which comprises reacting it with an organic boron represented by the formula (■) and then treating it with hydrogen peroxide.