JPS5962539A - Preparation of homoallyl alcohol - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as an intermediate for organic synthesis, etc., easily, by reacting an allyl compound with a carbonyl compound in the presence of non-ignitable easily-handleable metallic manganese, and hydrolyzing the reaction product. CONSTITUTION:The compound of formula III can be prepared by (1) reacting the allyl compound of formula I (R<1> and R<2> are H, alkyl or aryl; X is halogen, sulfonyloxy, or dialkoxyphosphinyloxy), with the carbonyl compound of formula II(R<3> and R<4> are H, alkyl or aryl, or R<3> and R<4> together form alkylene or alkenylene) in a solvent such as tetrahydrofuran at 0-150 deg.C in the presence of metallic manganese and preferably an activation agent, and (2) hydrolyzing the resultant reaction mixture. The manganese is powder having diameter of preferably 50-0.05mu, and its amount is 1-10mol per 1mol of the carbonyl compound.

Description

Detailed Description of the Invention H The present invention relates to a method for producing homoallyl alcohol represented by W (which together with W can form a dialkylene group or an alkenylene group; X is a halogen atom, a sulfonic acid ester group, or a 1d!J ester group).

The homoallyl alcohol represented by the general formula (I) published by the present invention has uses as an intermediate in organic synthesis (J, Am, Chem, Soc, 10
2.4548 and 7107 (1980)). It also has uses as an aromatic substance (Bond Patent No. 110.254
).

Conventionally, as a method for adding allyl anions to carbonyl compounds, a method in which allyl lithium or allyl magnesium bromide is applied (J, Chem, S -0C1, Pe
rkin), 1655 (1972) and 5ynthes
is347 (1971)), but these reactants were difficult to prepare and had problems in handling, such as being flammable. To overcome this drawback, a chromium reactant that is easy to handle and has high selectivity has been developed (Bull, Chem, Soc, Jpn, 55°561 (1982)). However, even this method uses 1/2 mole of expensive lithium aluminum hydride, and is not suitable for mass synthesis.

The present inventors have focused on manganese resources, which are said to be promising in the future, and have considered their synthetic use (see reference side). The present invention was completed by successfully adding an allyl group to a ketone or aldehyde by using the following.

In the present invention, in the presence of metal manganese, the general formula (wherein R1 and R2 are hydrogen atoms, alkyl groups, or aryl
l: halogen JjX, sulfonic acid ester group or phosphoric acid ester group. ) and the general J (where 1t5 and 1♂ are hydrogen atoms, alkyl groups, or aryl groups, and IIF and lt4 can be combined to form 9 alkylene 2+1j or an alkenylene group. )
The above general formula (1) is reacted with a carbonyl compound represented by the formula (1) and the resulting reaction mixture is hydrolyzed.
It is used to prepare homoallylic alcohol represented by

The allyl compound represented by the general formula (If) is i, I 5-furomoglopene, 6-iodopropene, 1
-bromo-2-butene, 1-iodo-2-butene, phosphorus-branched allyldiethyl, phosphorus-branched (2-butenyl)diethyl,
Examples include 1-bromo-6-mether-2-butene and allyl paratoluenesulfone.

The carbonyl compound represented by flfl Re general formula 011) includes alkanals such as acetaldehyde, propanal, and butatel, aryl carbaldehydes such as benzaldehyde, furfural, thiophene-2-carbaldehyde, and naphthalenecarbaldehyde, cyclohexanone, 2-octanone, Ketones such as tetralone can be mentioned.

It is preferable to use powdered manganese for use in the present invention from the viewpoint of high reactivity, and the particle size thereof is, for example, 5.
It is preferable to have a thickness of 0μ to 0.05μ. The amount used can be 11 to 10 times the mole of the carbonyl compound.

In order to perform the present invention with good yield, it is preferable to activate manganese, and as the activator, iodine, mercury, etc. may be used alone, or iodine and an aluminum halide such as diethylaluminum chloride may be used in combination. can.

The amount used can be the same molar amount as the so-called catalyst.

The present invention is preferably carried out in a solvent, such as an ether solvent such as tetrahydrofuran or dimethquinethane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or 1.3-)methylimidazolidin-2-one. Aprotic polar solvents can be used. The reaction takes place in the range of 1t from 0℃ to 150C.
It can be done in 11.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 H Manganese powder (10μ) 0.192 under argon atmosphere
g (5.5 mmol) and iodine 0.127 g (0.5
mmo! ) of THF (10rrIl) M suspension was stirred for about 2 hours and heated to reflux from the outside, and then allyl bromide 0.2
6m (mmol) and benzaldehyde 0.10
9m, i (1mm -01)'],'HF (5u
++/4) The solution was heated to reflux.

- After stirring overnight, add water to the reaction mixture, extract with ether, dry the ether layer with magnesium sulfate, condense, and purify by column chromatography (silica gel, ethyl acetate/hexane = 1:20 to 1:5). KotoKjt71-
Phenyl-6-puten-1-ol 0.12 g (yield 8
1) was obtained.

'H-NMR (CDC13): δppm 2.28 (
brs.

1)■), 2.53(t:J- 6,2H2,2Ll), 4.78( t: J = 5.811z, 1ll).

4.92-6.12 (m, 5) 1).

7.18-7.44 (m, 5H).

IR (neat): 34ro 0, 1640, 1050, 9
20°878.760,702cm-”.

MSm/e (te1%): 148 (M, none),
1 [J7(100), 77(33,6), 51(1
0,4), 41(5,9).

Example Manganese powder (10zl) 0.16 under argon atmosphere
5 g (mmol) and 5 g THF (10 ml) of mercury
)%'12 suspension was heated for about 2 hours, and then Tl-, LP (
5 mg) solution was heated to reflux/H3'-F'.

- Stir overnight, add water to the reaction mixture, extract with ether,
The ether layer was dried with magnesium sulfate, 1+A M6 and 2M chromatograph (silica gel).

1-Phenyl-6-puten-1-ol was obtained by purification with ethyl acetate/hexane (1:20 to 1:5).
126 g (85% yield) was obtained.

Example 6 Manganese powder (10μ) 0.192 under argon atmosphere
g (3.5 mmol) and iodine 0.127 g (0.5 m
After heating and refluxing a suspension of mol) in THF (10 m/) for about 2 hours with stirring, allyl bromide 0.26 a/'(
3 mmol) and 0.104 g (0.68 r
A solution of nmol) in THF (5 m7) was added dropwise while heating under reflux. - After stirring overnight, add water to the reaction mixture and extract with ether, dry the ether layer with magnesium sulfate, concentrate, and HH with column chromatography (silica gel, ethyl acetate/hexane - 1:20 to 1:5). Yoshi, 1
-(2,2,3-trimethyl-6-fuclobentene-1
-yl) -4-henten-2-ol 0.067g
(Yield -51 cm) was obtained.

1H-NMR, (CDCl 6) 2 δppm0, 7
7 (s, 5H).

1.00 (s, 5H,), 1.25-2.5 (m,
111-1), 4.69 (m, IH), 5.02 (m
, IH).

5.2 (m, 2H), 5.61-6.1 (m, IH).

11((neat):340D, 2975, 2925,
1640°1440.138 [], 990,910,8
00°580cm.

MSm/e (re1%): 194 (M'-, O), 15
5(16).

109(86), 108(100).

43 (30), 41 (57).

Examples 4 to 17 H Otori (1) Under the same conditions as in Example 1, various allyl bromides (2) were reacted with aldehydes or ketones. The results are shown in the table below.

Example 18 - OP (OE t ) 2 + Otori CHO Under argon atmosphere, manganese powder (10μ) 0.385. ! 7 (7m
mol), iodine 0.254g (1mmol I)
and diethylaluminum chloride (15% Hexane solution) of Tf(F (2
0ml)lIw! After heating and refluxing the whole suspension for a while while stirring, 1.17 g of allyl diethyl phosphate (6 mmo
+ ) and benzaldehyde [1,1(12+117'
A solution of (1,0 mmo + ) in THF (10 ml) was added dropwise under heated R flow. - After stirring overnight, water was added to the reaction mixture and extracted with ether. The ether layer was dried with magnesium acetate, condensed (1+, 4), and subjected to column chromatography (silica gel, ethyl acetate/hexane - 1:2U to 1:5 )
1-F22RO-butene-1-
60 mJ of all (yield 41%) was obtained.

“Reference example: Manganese chloride 4110.503 g under argon atmosphere
(4,00 mmo 1 ) in THF (10y) under ice cooling, LiAlH40,152,! 9 (4,00mm
After stirring for 30 minutes under water cooling and 1 hour at room temperature,
Allyl bromide 0.174 mg (2,00 mmo I) O
A THF (5ml) solution was added dropwise at room temperature. After stirring for 1.5 hours, 0.274 g (1,41 mmol) of 2.2.3-trimethyl-6-cyclopenten-1-ylethanal was added.
) in THF (5 ml) was added to the mixture, and the mixture was further stirred for 1.5 hours. Water was added to the reaction mixture, extracted with ether, and the ether layer was dried with magnesium sulfate, condensed, and purified by column chromatography (Nrica gel, ethyl acetate/hexane = 1:2 (1:2) to 1:5). 1-
(2,2゜3-methyl-cyclopenten-1-yl)-4-penten-2-ol 0.146 g
(53%).

Patent Applicant Procedures Amendment ■(Voluntary) 31st lθ, 1980/l-nrt'r Agency J Soki Kazuo Wakasugi j7 City Display Show; tl+ 57 'rEIP! j Fr Application No. 1639
51 No. 2o Invention Name 1 Method for producing homoallylic alcohol 31. Supplementary iF: "Claims" and "Detailed Description of the Invention" of the specification of the applicant
Column 5, Contents of amendment (1) The present application is clear, j + page 1, line 5 ~ ε1) 2
The "Scope of Claims" section on page 12 is revised as follows.

"(1) In the presence of gold 2.4 manganese, an allyl compound represented by the general formula and a carbonyl compound represented by the general formula are reacted, and the resulting reaction mixture is hydrolyzed. A method for producing homoallylic alcohol (in the formula,
R' and 112 are hydrogen atoms, alkyl groups or aryl groups, and R3 and xN are hydrogen atoms, alkyl groups or aryl groups! , , n5 and male can be combined to form an alkylene group or an alkenylene group.

x is a halogen atom, a sulfonyloxy group or a 1d9 alkoxyphosphinyloxy group; ).

(2) Consists of using an activator together with metal manganese,
A method according to claim (1).

(3) The method according to claim (2), wherein the activator is iodine, iodine-aluminum halide, or mercury. ” (2) “L sulfonic acid ester group” on page 3, line 4 of lJF’ was corrected to “sulfonyl oxy 7 group” and line 1 of lines 4 to 5 was corrected.
"phosphate ester group" is corrected to "dialkoxyphosphinyloxy group".

(3) Delete "(See reference side)" on page 4, line 8.

(4) Delete page 16, line 2 to page 17, line 5.

that's all

Claims (1)

[Claims] (1) Reacting an allyl compound represented by the general formula with a carbonyl compound represented by the general formula in the presence of metallic manganese; 1.1 Hydrolyzing the preferred reaction mixture once; Method for producing homoallylic alcohol represented by karana 11 (in the formula,
R1 and R2 are hydrogen atoms, alkyl groups or aryl groups,
(3 and 1v are a water atom, an alkyl group, or an aryl group, and (3) and R4 together may form a dialkylene group or an alkenylene group. X is a halogen atom, a sulfonyloxy group, or a bosphinyl group. ). (2) Consists of using an activator together with metal manganese,
The method described in item (1) of the scope of patent hr1. (6) The method according to claim (2) JA, wherein the activator is iodine, iodine-aluminum halide, or mercury.