JPS5910538A - Preparation of propargyl type alcohol - Google Patents

Abstract

PURPOSE:To obtain the titled various compounds useful as a perfume, or an intermediate for other perfumes, medicines or agricultural chemicals without the limitation on the structure, by reacting an allyl Grignard reagent with ethynyl ketone. CONSTITUTION:A compound of formula I (R<1> and R<2> are H, alkyl, cycloalkyl, alkenyl or aryl or together with the carbon atom to which they are linked form a ring; R<3> is H or lower alkyl; X is Cl, Br or I) is reacted with ethynyl ketone of formula II (R<4> is alkyl, cycloalkyl, alkenyl or aryl, etc.) at -10-+30 deg.C to give the aimed compound of formula III. Infinitely various propargly type compounds can be easily obtained without the following limitation of the conventional method when the (iso)mesityl oxide is used as a raw material: The (iso) mesityl oxide has the methyl groups at the 3- and 5-positions of the basic skeleton and one hydrocarbon group at the 4-position thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing glopargyl alcohol represented by general formula (1).

In the above general formula (1), R1 and R2 are the same or different, hydrogen atom: methyl group, ethyl group, propyl group, butyl group, 3-methylbutyl group, pentyl group, octyl group, 3,7-dimethyl Alkyl groups such as octyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, menthyl group; vinyl group, 1-propenyl group, allyl group, isopropenyl group, 2-methylallyl group, 1-butenyl group, 2-butenyl group , geranyl group, 3-methyl-3
-butenyl group, 2,3-dimethyl-2-butenyl group, 3
-Methyl-2-pentenyl group, 3-methyl-3-pentenyl &, 3+ 7- dimethyl-2-octenyl group, 3
, 7-dimethyl-6-octenyl group, geranyl group, 3-
Alkenyl groups such as ethyl-7-methyl-2,6-nonajenyl groups: or phenyl groups, tolyl groups, xylyl groups,
Represents an aryl group such as a naphthyl group. Also R1 and R2
and may form a ring together with the carbon atom to which they are bonded. R3 represents a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and R4 represents a methyl group, an ethyl group, a propyl group, a butyl group, a 3-methylbutyl group, a pentyl group, an octyl group,
3. Alkyl group such as 7-dimethyloctyl group; cycloalkyl group such as dichloropentyl group, cyclohexyl group, menthyl group; vinyl group, 1-furohenyl group, allyl group, in70 benyl group, 'l.

-methylallyl group, ■-butenyl group, 2-butenyl group,
Geranil! , 3-methyl-3-butenyl group, 2.3-dimethyl-2-butenyl group, 3-methyl-2-pentenyl group, 3-may-3-pentenyl group, 3.7-')
Methyl-2-octenyl group, 3,7-dimethyl-6-octenyl group, geranyl group, 3-ethyl-7-methyl-2
, 6-nonajenyl group; cycloalknyl group such as 2-cyclopentenyl group, 3-cyclopentenyl group, 2-cyclohexenyl group, 3-'/C7 hexenyl group: phenyl group, tolyl group, xylyl group group, aryl group such as naphthyl group; or benzyl group, 1-
Phenylethyl group, 2-phenylethyl group, 1-7enylglobyl group, 3-7enylprobyl group, 2-methyl-
It represents an aralkyl group such as a 1-7enylprobyl group or a 2-naphthylethyl group.

The glopargyl alcohol represented by the general formula (1) is
This esterification reaction with all organic carboxylic acid anhydrides or A
By subjecting it to the Xycope rearrangement reaction, esters or α, β-・γ, δ-unsaturated ketones and α, β-, δ, ε-unsaturated ketones
(See Publication No. 7906).

Conventionally, glopargyl-type alcohols having a hex-1-yn-5-en-3-ol skeleton have been produced by reacting mesityl oxide or disomesityloquinde with a nonlogeno hydrocarbon in the presence of an alkaline condensing agent. It is produced by preparing a β, γ-unsaturated chotone substituted with a hydrocarbon group at the position and then ethynylating it (JP-A-52-93
Reference No. 707 Akihito's conventional method is excellent as an industrial method for producing the pr1 pargyl alcohol because it uses inexpensive mesityl oxide or isomesityl oxide as a raw material and is easy to operate. ,On the other hand,
Propargyl-type alcohols produced depending on the raw materials used are limited to those having methyl groups at the 3- and 5-positions of the basic skeleton and one hydrocarbon group at the 4-position. Therefore, it is not suitable for various glopargyl-type acicols up to M.

As a result of thorough investigation to solve the above-mentioned problems in conventional methods using mesityl oxide or imesityl oxide as a raw material, this Q'114 et al. A method for easily producing pargyl-type alcohol was discovered, and the present invention was achieved.

That is, according to the present invention, ~.general formula (II) [wherein,
R1, It2 and R3 are allyl Grignard reagents represented by the general formula (1).
'-C-C藉CH・・・・・・(III)- [In the formula, R4 has the same taste as in the general formula (dish). By reacting with ethynyl ketone represented by J, the propargyl type alj-l represented by the general formula (1) can be produced.

-71J Le Grignard reagent d1 of general formula (II) corresponds. Trihalate and metallic magnesium are mixed together in a JJ atmosphere at 0°C to 50°C in an ether solvent such as tetrahydrofuran or diethyl ether.
C. Preferably, it can be prepared by reacting at a temperature of -5°C to 30°C. The time for this reaction is considerably influenced by the type of allyl halide and the reaction temperature, but is usually about 1 hour. This reaction system has the general formula (
In) ethynyl ketone 'fc-30C~50
A tr reaction mixture containing a glopargyl type alcohol represented by the general formula (1) is obtained by dropping it dropwise at a temperature of preferably -10°C to 30°C and stirring at that temperature or at room temperature -F for about 1 hour. It will be done. Glopargyl type alcohol can be separated and recovered from this reaction mixture by a conventional method. For example, an aqueous hummonium chloride solution is added to the reaction mixture, followed by extraction with diethyl needles, etc., the extract is washed with water and dried, the solvent is distilled off, and the remaining oil is used for distillation or chromatography. It can be represented by the general formula CI). A pargyl type alcohol can be obtained. The present invention will be specifically explained with reference to the following examples. While maintaining the internal temperature at about 25° C., 6.39 F of brenyl chloride was gradually added dropwise to the bottom of the solution to prepare a Grignard solution. Next, Echini/L/n
- Globilke) 72.35 f (purity 86.2%)
A solution of 10 ntl of 1 trahydro7 is endothermally 25
'C. After stirring for 1 hour at the same temperature, a small amount of saturated ammonium chloride aqueous solution was added dropwise to the reaction mixture, and the solution was then removed using a natrahydrofuran evaporator. The residual liquid was poured into a large amount of saturated ammonium chloride water #I, extracted three times with 11-hexane, the extract was washed with water, and further dried over anhydrous tutria sulfate. N-hexane was removed from this extract using an evaporator, and the remaining liquid was distilled under reduced pressure to obtain a fraction of 90-bw+HF. 3 in-5-en-3-ol
．． 31t (purity 82.1%) was obtained. Yield: 79 cm.

The physical properties of the product are shown below.

Mass, r+1/e: 166 [M,]
! iR(down-') =3480.3300.31J8
0.2960.2940°2880, 1640.14'
75.1380.1010°20 2.40 (s, l II, -C tumor CH).

4.9 to 5.2 (m, 2H, /=CH2).

5.9-6.3 (rn, IJI, -11C=) Example 2 100r! Metallic magnesium 0 in L/3-capacity flask
, 63F and 40 tl of dry tetrahydrofuran, and keep the internal temperature at about 25℃ under nitrogen atmosphere.
2.36 f'i of lyl chloride was gradually added dropwise, and the Grignard solution was poured into the solution. Then, a solution of 1.0 f (Nf 100%) of ethynyl n-probyl ketone in 5 d of tetrahydrofuran was added dropwise (-
1. Stirred at the same temperature for 1 hour. A small amount of saturated ammonium chloride aqueous solution was added dropwise to the reaction mixture, and then tetrahydrofuran was removed from this solution using an evaporator [7]. The residual solution was poured into a saturated aqueous solution of ammonium chloride overnight, extracted three times with n-hexane, the extract was washed with water, and further dried over anhydrous sodium sulfate. n from kernel extract
--, xane was removed using an evaporator, and the remaining liquid was subjected to column chromatography (developing solution: ethyl acetate and n-
By volumetric hexane 1:10 mixture),
3-n-propyl-5-methyl-hex-1-yn-5
-xy-3-ol fc1.54y (purity 90.8%)
Obtained. Yield 89%. The physical properties of the product are shown below.

MaRs, rv/e: 152 CM) Sat IR (r
yy++') :3440.3300.3080.2
960.2880°1650, 1460.1380.1
030.9002.37(s, 2H, -Cr12A
).

2.40 (+!, IH, -CyCH).

4.83.4.96 (each bs, 2H, -C
-CH2) Example 3 3-ethyl-4,4-dimethyl-hex-1-yn-5
Synthesis of -en-3-ol (methallyl chloride 2.36 at 3'132)
Using brenyl chloride 3,19fi instead of 9, nib-nyl n-)゛rovirctone 1. (3-edyru 4.4-
2.20 r of dimethyl-hex-1-yn-5-en-3-ol (purity 77.4 t) was obtained. Yield 92%. The physical properties of the product are shown below.

Mass, +Iye: 152 [M,]1shil1l
ctn-”): 3500, 3300, 3080, 298
0,2940°28B0.1640.147(1,14
20,138 (1°1360, 1100.1010.9
60.9202.40 (s, ln, -C CH).

4.94-5.21 (m, 2H, -C=CH2).

5.94-6.32 (m, 111.-CH=)
Example 4 In Example 2, 2,3-dimethyl-2-butenyl chloride instead of methallyl chloride 1''2.36r: 3.
By carrying out the reaction and separation and recovery in the same manner except that 09 Y was used, 3-n-propyl-4,4°5-trimethyl-hexar J-yn-5-en-3-ol, total 1.
70f (pure Fki74 was obtained. Yield: 67%. The physical properties of the product are shown below.

Mass, m/e t 180 (Ni'J!If shell example-1) heat 3540.3310.3090.2960.
2940°2880, 1630.1450.1380.
9002.38 (S, 1st leg-C so-called CH).

4.90. 4.98 (each bs, 24LC=
Cf(2) Example Reaction and separation and recovery were carried out in the same manner as in Example 2 except that 3.7-;methyl-2,6-octazininyl chloride 4.47+7ffi was used instead of 2.36 f of methallyl chloride. By performing 3-n-propyAy -4
-7f /17-4metsut7yu7. -2.542% of 1-yen-5-en-3-ol (purity 89.2%)
)Obtained. Yield 9:3. The physical properties of the product are shown below.

Mass, m7e: 234 (M)'.

111(c,7+')::150U,3310,308
0,2960,2930°2880,1670.164
0.14(i('l, 1380°3110, l(+
70.1. (11,0,920CI)U3H'-NMR (δ): lum 2.4'O(s, LH, -C4CH).

4.90-5.34 (m, 311. A>c■lz,
to CH2).

5.73-6.22 (m, LH, -CH=) Examples 6-13 Various (7) y + 7 = Yare reagent (■) and ethynyl ketone (Ill) under the same conditions as Example 2 Glopargyl type alcohol (1) was obtained by the reaction described below.

The results are shown in Table 1.

Reference Examples 1 to 5 (Vl) lv of the globargyl type alcohols obtained in Examples 1 to 5
rl was dissolved in N-methylpyrrolidone 3we and heated at a temperature of 175±2° C. for 5 hours under nitrogen atmosphere. The reaction mixture was then poured into a large amount of water and extracted with n-hexane. The extract was thoroughly washed with water and then dried over anhydrous sodium sulfate. N-hexano was removed from this extract using an evaporator, and the remaining oil was subjected to column chromatography (developing solution: a mixture of ethyl acetate and hexane).
This gave a mixture of cine-saturated ketones. The total yield and isomer distribution of unsaturated ketones are shown in Table 2. In addition, formulas (IV), (V) and (Vl) in the above 1 are cis,
It does not even specify the configuration of trans.

Claims (1)

[Claims] General formula (wherein R1 and R2 are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and R1 and R2 are the bond 1-1
may form a ring together with other carbon atoms. R8 represents a hydrogen atom or a lower alkyl group, and X represents a chlorine atom, a bromine atom or an iodine atom. ) is reacted with an ethynyl ketone represented by the general formula % (wherein R4 represents an alkyl group, a cycloalkyl group, an alknyl group, a cycloalkenyl group, an aryl group, or an aralkyl group). A method for producing a glopargyl-type alcohol represented by the general formula % (4 (wherein 4-1, R2, R3 and R4 are as defined above).