JPS60126279A - Tricyclic epoxide - Google Patents

Abstract

NEW MATERIAL:2,6-Epoxytricyclo[5.2.2.0<2>,<6>]undecane of formula I . USE:Useful as an aromatizing agent for perfume compositions, and having particularly strong camphorlike aroma. PREPARATION:Tricyclo[5.2.2.0<2>,<6>]undec-2(6)-ene of formula II is reacted with a peracid, e.g. perphthalic acid or peracetic acid, to epoxidize the internal olefin and give the aimed compound of formula I . The compound of formula II is obtained by reacting 2-hydroxy-tricyclo[5.2.2.0<2>,<6>]undecane with p-toluenesulfonyl chloride in the presence of pyridine or dehydrating the above-mentioned 2-hydroxy-tricyclo[5.2.2.0<2>,<6>]undecane in the presence of a dehydration catalyst, e.g. ''Amberlyst 15''.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel bicyclic epoxide, 2,6-epoxide dicyclo(5,2,2
, 0) regarding undecane.

It has been reported that some tricycloundecane derivatives are useful as flavoring ingredients for perfume compositions (I￥f Publication No. 10139, No. 53-3, Japanese Patent Publication No. 53-3).
No. 5141, JP-A-55-11590, JP-A-57-
No. 114539, etc.).

Unexploded BA researchers synthesized various new tricycloundecane derivatives and studied their physical properties, and as a result, the above (
1) 2,6-epoxide dicyclo(5,
2,2,0) He discovered that undecane has a strong woody, camphor-like aroma, and completed his invention.

Therefore, the present invention provides a novel 2,6-epoxide dolicyclo(5,2,2,0)undecane (1) which has an excellent woody, camphor-like aroma and is useful as a flavoring ingredient. It is something to do.

The compound (1) of the present invention can be produced, for example, by the following reaction formula (according to the following reaction formula, tricifo(s,zzo)undec-2(6)-ene(
[) with peracid to epoxidize the internal olefin (prepared from 2).

01) (I) The raw material tricyclo(5,2,2,0'')undec-2(6)-ene0) of the present method is, for example, 2-hydroxy-tricyclo(5,2,2,0) Undecan 0101=
The main product of the olefin mixture can be obtained by reacting with P-)luenesulfonyl chloride in the presence of pyridine or by dehydrating it with a dehydration catalyst such as Amberlyst 15.

(II) Examples of the filtration acid used in this method include per7talic acid, peracetic acid, perbenzoic acid, metachloroperbenzoic acid, and the like. The reaction is generally carried out under moxibustion conditions that are used when epoxidizing olefins. Note that even if the raw material contains isomers of olefins other than compound (If), compound (n) is The amount of peracid used can be adjusted (thus, to obtain the selective C-dual compound (I) t:).

The non-invention will be explained below with reference to examples and reference examples.

Reference example 1゜tricyclo(5,2,2,0'')undec-2(6)
-Ene (■): 2-hydroxytricyclo(5,2,2,0) run f
ly 7(2) 1.66f (10 mmol) was dissolved in 10 l of n-hexane, and this (Niamberlyst-1
Add 50,331. The reaction solution is heated to reflux for 45 minutes to remove Amberlyst-15. The n-hexane layer is washed with a saturated sodium bicarbonate aqueous solution and then dried over anhydrous sodium sulfate. After distilling off the solvent, it is purified by silica gel column chromatography. Tricyclo(5,2,2,0)unodeku2 as n-hexane eluate
(6)- and 2(3)-ene mixture O193F (6
, 3 mmol, yield 63 buns). Next, 0.1'1 (
Collect 10 pieces of raw material (2). The production ratio of 2(6)-ene and 2(3)-ene was determined by gas chromatography to be 70:30.

Boiling point = 41℃/0.4 mmHg elemental analysis value (C
X1 ■116) Calculated value (@: C,89,1+ 11.10.9 Actual value (%): C,89,01) )-ene form, for example, is detected by gas chromatography at an early stage of sheath dehiscence.

IR (liquid film, cm-”): 2(6)-ene form (11) 2950, 2860. 2850. 1450. 1
315°1005, 850. 800 2 (3) = En body 2940, 2860. 2850. 1450. 1
340°1275, 1245. 1180. 111
0. 1055°970, 900. 800. 78
52 (G) -, In/body (It): 0.90
-2.68 (complex multiline) 2(3)-ene body: 1.01-2.78 (13H, complex multiline I (line) 5.
14-5.39 (IH, complex multi-M disappearance)”C-NMR
(CjJCl, solvent, TM8 internal standard, δC):2(6
)-en body (ffn: 23.6(n, 26.7(t,
4.

31.2 (d, 20) e32.9 (“120).

142.3(s, 20) 2 (3) -x :y body: 21.0(t), 2
4.4(su, 26.3(su).

29.8 (2t+d, 3G), 30.9 (d几31.
9(t).

48.8(d), 117.5(d), 153.4(
s) GC-MS (S., Relative intensity n2(6)-ene body (It) 148 (Δf'', 17), 120 (100), 105
(14)92(41), 91(59), 79(10).

77(9), 65(7), 51(7), 41(15)2
(3) -en body 148 (M+, 55), 120 (91), 119 (47
).

105 (38), 94 (37) f 91 (1003°8
0 (44), 79 (70), 77 (35).

41 (49) Example 1゜2.6-Epoxide dicyclo(5,2,2,0'') undecane (■): Tricyclo(5,2,2,0) undec-2 obtained in Reference Example 1 (6)-Ene (li) 1.48f (10 mmol)
and 2.5 tsl of metachloroperbenzoic acid and 2.5 tsl of metachloroperbenzoic acid at 0-5° C. without stirring.
A solution consisting of 60,115 mmol) and 25 ml of chloroform is added dropwise over a period of 20 minutes. After the reaction is completed, the mixture is washed twice with IJ sea urchin solution (25%), then washed with water, and then dried over anhydrous sodium sulfate. Chloroform was distilled off and purified by silica gel column chromatography (second step. 2,6-epoxide dicyclo (5,2°2
．． 02″6〕 Undecane (1) 1.60′l (
9.6 mmol, yield 96%).

Original cumulative analysis value (as C□IH160) Calculated value (inquiry: Cl2O, 41H#9.8 actual measurement value (working:
e, 80.1, I-1,9,9I R (liquid film, Cm-"): 2950, 2880. 1455. 1420. 1
365°1335, 1305. 1285. 121
0. 116 (1°104L 920.880.8
60. 810. 795°60') l-NMR (CDCI, solvent, 'I' M8 internal standard, δ) 0.95-2.29 (complex multiplet) 'C-NMR (CDCI, solvent, '1' MS internal standard ,
δC)21.4(t), 23.1(t, 20)t
24.2 (t, 20).

27.6 (t, 20), 29.5 (d#20),
67.2 (8,20) 110 (85), 95 (36),
91(35).

80 (41), 79 (53), 55 (41), 41 (7
3) Patent applicant: Kao Soap Co., Ltd. Agent Mochizuki Keibe

Claims (1)

[Claims] 1. 2,6-evo-citricyclo(5,2,2
,0""6] Undecane.