DE2319783C3 - Sulfones containing a methyl pentenyl chain - Google Patents

Description

15th

in which one of the radicals Y and Yi is a hydrogen atom and the other is a methyl radical, R and Ri, which can be the same or different from one another, are each -COCHs, -COOCH3, -COOC2H5 or -CN, Q is a phenyl- or a terpene radical with a number of carbon atoms of 5 n, where π can be from 1 to 9 , wherein its radical can be saturated or unsaturated, conjugated or non-conjugated polyenic, or substituted by alkyl groups and where, if π is 2 or more, Q can comprise a ring to which alkyl groups and / or = O or -OH, which in turn can be free or protected, can be bonded.

25th

2. Process for the preparation of compounds according to claim 1, characterized in that one in the presence of a basic agent, a diene sulfone of the formula

Q- SO2- CH = CY- CYi = CH?

with a methylene compound of the formula R — CH2 — Ri, where the symbols Q, Y, Yi, R and Ri have the meanings given above.

3. Process for the preparation of compounds according to claim 1, characterized in that one in the presence of a basic agent, a halogenated sulfone of the formula

Q-SOz-CH ₂ -CY = CYi-CH ₂ X

with a methylene compound of the formula R — CH2— Ri, where the symbols Q, Y, Yi, R, Ri and X have the meanings given above.

4. Use of the compounds according to claim 1 for the synthesis of polyisoprene compounds.

The invention relates to sulfones containing a methylenepentenyl chain and having the general formula

Q-SO ₂ -CH ₂ -Cy = CY ₁ -CH ₂ -CH

(D

R ₁

correspond in which one of the radicals Y and Yi is a hydrogen atom and the other is a methyl radical means.

R and Ri, which are the same or different from one another each mean —COCH3, —COOCH3, -COOC2Hs or-CN.

Q denotes a phenyl or a terpene radical with a number of carbon atoms of 5 n, where η can be from 1 to 9; this radical can be saturated or unsaturated, conjugated or non-conjugated, polyenic, or substituted by alkyl groups; if π is 2 or more, Q can comprise a ring to which alkyl groups and / or = 0 or -OH, which in turn can be free or protected, can be bonded.

The compounds of the formula I can be prepared in various ways, in particular from compounds of the formula R — CH ₂ —Ri and compounds which have a sulfonic function.
One of these ways is to combine the compound R — CH2 — Ri with a halosulfone of the formula

Q-SO2-CH2-CY = CYi-CH2X

in the presence of a basic agent, which can be inorganic or organic, to implement. The reaction can be represented by the following scheme:

/ Q-SO ₂ -CH ₂ -CY = CY ₁ -CH ₂ X + R-CH ₂ -R ₁ - »Q-SO ₂ - -CH ₂ -CY = CY ₁ -CH ₂ -CH + HX

R,

The halogen sulfones used are in particular the chlorosulfones and the bromosulfones, such as l-chloro-2-methyl-4-phenylsulfonylbutene- (2) or 1-chloro-3-methyl-4-phenylsulfonylbutene- (2).

The compounds R — CH2 — Ri, which activated one Have methylene group, malonic acid derivatives, such as malonic acid esters, malonitrile, acetylacetone, Acetyl acetic acid esters or alkyl cyanoacetates.

Among the basic agents that may be suitable are the alkali hydroxides and carbonates, which Alkali alcoholates and organic bases, such as the amines, name.

The reaction is preferably carried out in a solvent such as an aliphatic alcohol, an ether

or an aliphatic or aromatic hydrocarbon, a beneficial agent for Carrying out the reaction consists in being basic Means to use an alcoholic solution of an alkali alcoholate.

connection R — CH2 — Ri with a diene sulfone of formula

Q-SCh-CH = CY-CYi = CH ₂

in the absence of a basic catalyst according to

Another of these ways is to implement the methylene according to the following scheme:

Q-SO ₂ -CH = CY-CY ₁ = CH ^ r-CH ₂ -R ₁ -Q-SO ₂ /
CH ₂ - CY = CY, - CH ₂ - CH

Among the dienesulfones suitable for this reaction one can use the 4-alkyl (or aryl) sulfonyl-2-methylbutadienes, the 4-alkyl (or aryl) -sulfonyl-3-methylbutadienes, the 4-isoprenylsulfonyl-methylbutadienes, the 4-geranylsulfonyl-methylbutadienes, and the 4-retinylsulfonyl-methylbutadienes to name. These dienesulfones can be obtained by reacting an alkyl halide Q-X with an alkali metal isoprenyl sulfinate by one of the usual methods for the preparation of sulfones getting produced.

The reaction between the dienesulfone and the methylene compound is in the presence of inorganic or organic alkaline agents such as alkali hydroxides or alcoholates, amines, e.g. B. Diethylamine, diisopropylamine, pyridine, triethylamine and tributylamine or quaternary ammonium hydroxides, carried out The reaction can be carried out with or without a solvent. However, it is preferred to choose a solvent such that the reaction proceeds in a homogeneous phase. This solvent can be an alcohol such as methanol, ethanol or tert-butyl alcohol, or an ether such as ethyl ether, Dioxane or tetrahydrofuran, or any other inert solvent such as benzene, toluene, dimethylformamide or acetonitrile.

The reaction takes place at room temperature. If the reaction product (s) does not occur by heating can be changed, the reaction can be accelerated by using higher temperatures. When the reaction products are sensitive to heat, you can work at temperatures below room temperature. In "Organic Reactions, Vol. 10, pp. 264 to 266, The Michael Reaction," is a compilation of the Working conditions that affect the Michael reaction, of which the present process has an application represents.

In addition to their sulfonic functions, the compounds according to the invention contain one of the functions listed above for R and Ri and are therefore suitable for the synthesis of polyisoprene compounds of various degrees of saturation, which belong to geraniol, ionones and pseudoionones, retins or apocarotenes. The compounds according to the invention create new ways of preparing d (n + ;; compounds, starting from Cs _n compounds, the reactions being considerably simpler compared with previous methods.

For example, with the compound obtained according to Example 9, it is possible to use the phyton, the in turn can be converted into phytol, which is one of the starting materials for the synthesis of vitamin E, by simple desulfonation and decarboxylation. The following is that Reaction scheme for the production of phyton,

'5 indicated starting from dehydrolinalool, on the one hand via the compounds obtained according to the invention and on the other hand in a known way. It can be seen that access via the compounds according to the invention is much easier than was previously possible:

a) Procedure using
of a sulfone according to the invention

1. Effect of phosphorus tribromide on dehydrolinalool- »geranyl bromide,

2. Condensation of geranyl bromias with an alkali metal-2-methylbutadienyl-sulfinate -► sulfone the formula

so,

3. Reaction of this compound with ethyl acetoacetate according to Example 9,

4. Decarboxylation and desulfonation of the product obtained to give phyton.

Thus, starting from dehydrolinalool, a condensation occurs via the products according to the invention. Cio + C5 = Ci5 and then via the acetylacetonate, condensation = Ci8 possible due to decarboxylation.

35

40

b) Known procedure

1. Dehydrolinalool + diketene, by CAROLL reaction - »pseudoionone (condensation C10 + C3),
2. Ethynylation of this ketone via magnesium compounds - ■ ► acetylenic cis-carbinol (Cn + C ₂ ),

3. selective reduction to cis-vinyl carbinol,
4. Renewed CAROLL reactions on the carbinol

-► Ct8 ketone (Ci5 + C3).

In this way the cis-ketone, starting from Dehydrolinalool produced in four stages by reactions different from the above and are more difficult to perform than these.

example 1

In a held at 25 ⁰ C i flask are introduced, 08 g of l-phenylsulfonyl-2-methylbutadiene, 1,5 g redistilled Äthylacetylacetat (Kpi, 5 = 70 ^c C), 0.4 cm ³ of a methanol solution containing 40% Trimethylbenzylammoniumhydroxyd and 40 cm ^{3 of} acetonitrile. The mixture is kept under a nitrogen atmosphere with stirring overnight. It is then diluted with 200 cm ^{3 of} water, neutralized with acetic acid, then extracted three times with ethyl ether and washed three times with a saturated sodium chloride solution. Then the reaction

mass over magnesium sulfate and remove the solvent in a vacuum. 3.56 g of a crude residue are thus obtained, which can be isolated by thin-layer chromatography (Carrier: silica; eluent: methylene chloride / cyclohexane in a volume ratio of 50:50) 132 mg of a product of the formula

C "H ₅ -SO, -CH ₂ -C (CH,) = CH - CHy-CH (COCH.,) - COOC ₂ H ₅

isolated The yield is 27%.

The l-phenylsulfonyl-2-methylbutadiene was after that in Journal of Organic Chemistry, 35, p. 4219 (1970), described method produced

Example 2

0.2 g of a methanolic solution containing 40% trimethylbenzylammonium hydroxide is added to a solution of 1.13 g of ethyl cyanoacetate in 10 cm ^{3 of acetonitrile.} It is cooled to 10 ^° C. and brought within 10 minutes

"5 a solution of 2.08 g of 1-phenylsulfonyl-2-methyIbutadiene in 7 cm ^{3 of} acetonitrile eia

The temperature is allowed to rise to 23 ° C. and the reaction mass is left with stirring for several hours. They are then poured into a mixture of 70 cm ^{3 of} water and 30 cm ^{3 of} ethyl ether. The combined ether layers are washed with water. Dried over magnesium sulfate, filtered and concentrated. A viscous, uncolored product is obtained in this way, which is 2.6 g of a sulfone or formula

C "H ₅ —SO ₂ -CH ₂ —C (CH,) = CH — CH ₂ —CH (COOC ₂ H ₅ ) -

contains. The degree of conversion is 100% and the yield, based on the starting sulfone, is 81%.

Example 3

^{0.650 g (5 × 10 -3} mol) of ethyl acetylacetate and 10 cm ^{3 of} acetonitrile are placed in a 50 cm ^{3 three-} necked flask equipped with a stirrer, a condenser, a dropping funnel and nitrogen circulation. 0.250 g of a methanolic solution with 40% trimethylbenzylammonium hydroxide in solution in 3 cm ^{3 of} acetonitrile is added at + 20.degree.

The mixture is cooled to + 10 ° C. and a solution of Ig (5 · 10 ^-3 mol) sulfone of the formula is brought within 10 minutes

CH ₂ = CH -C (CHI CH — SO ₂ —CH, - -CH,

in 5 cm ³ acetonitrile. Is maintained for 50 minutes at + 10 ⁰ C and then for 3 hours at 23 ° C.

The reaction mass is poured into a mixture of 25 cm ^{3 of} water and 25 cm ^{3 of} ether. It is decanted and extracted twice with 20 cm ^{3 of} ether each time. The ether layers are washed three times with 20 cm ^{3 of} water each time, dried over magnesium sulfate, filtered and concentrated.

A whitish liquid is obtained which contains 0.460 g of unconverted sulfone and 0.800 g of the product formula

SO,

COOC ₂ H ₅

CH

COCHj

in the same manner, thus isolating 1.04 g of an off-white liquid product of the formula

35 SO ₁ - '

CH (COOC ₂ H ₅ ),

contains. The degree of conversion of the starting sulfone is 54% and the yield based on the converted sulfone, 90%.

The starting sulfone was obtained by adding 2.98 g of l-bromo-3-methylbutene- (2) to 2.64 g of l-dioxy-2,5-dihydro-3-methylthiophene (or cyclic isoprene sulfone) in the presence of 2, 24 g of potassium tert-butoxide in 20 cm ^{3 of} tetrahydrofuran and subsequent heating at 70 ° C. for 4 hours were prepared.

Example 4

The previous example is followed and 0.80 g of ethyl malonate is reacted with 1 g of the same sulfone in 10 cm ^{3 of} acetonitrile and the same amount of trimethylbenzylammonium hydroxide in methanolic solution. The reaction mass is then treated in The degree of conversion of the starting sulfone is 100% and the yield is 57%.

Example 5

26 g of ethyl acetylacetate are added to 200 cm ³ with 4.6 g

metallic sodium treated ethanol. The mixture is kept stirring for 30 minutes and then 24.5 g of phenyl-4-chloro-2-methylbutene- (2) -ylsulfone in solution in 200 cm ^{3 of} ethanol are added. The mixture is left with stirring at 25 ° C. for 1 hour and then refluxed for 2 hours. The ethanol is evaporated in vacuo and the residue is taken up in water and then extracted with ether. It is washed with a saturated sodium chloride solution until neutral, dried over magnesium sulfate and then evaporated. 32.6 g of a solid product are obtained in which 84% of the same compound as that obtained in Example 1 is determined by thin layer chromatography.

The phenyl-4-chloro-2-methylbutene- (2) -yl-sulfone was by the method described in Journal of Organic Chemistry, 35, 4218 (1970).

Example 6

A mixture of 1.32 g of methyl malonate, 10 cm ^{3 of} methanol and 0.23 g of sodium is heated at 60 ° C. for one hour while stirring. After cooling, 2.44 g of phenyl-4-chloro-2-methylbutene- (2) -yl-sulfone, diluted in 10 cm ^{3 of} methanol, are added and the mixture is kept at room temperature for several hours with stirring

Methanoi, takes up in water and extracted three times with 50 cm ^{3 of} ethyl ether. From the combined ethereal layers treated as in the previous examples th one isolates a crystallized product from M.p.-58 ° C, which is identified by IR and NMR spectrography and has the formula

C ₁₁ H ₅ -SO, -CH ₂ -C (CH ₁ I = CH-CH ₂ -CH- (COOCH ₃ I ₂

is equivalent to

Example 7

Under conditions identical to those of Example 1, 03 g of methyl malonate and 1 g of 1-phenylsulfonyl-2-methylbutadiene are placed in 10 cm ^{3 of} acetonitrile in the presence of 0.1 g of trimethylbenzylammonium hydroxide. The reaction mass is then poured into ice water and extracted three times with 50 cm ^{1 of} ether each time. By treating the combined ethereal layers, a product with a temperature of 58 ° C is isolated, which corresponds to the following formula:

Example 8

5 g of acetylacetone are introduced into a sodium ethylate solution of 50 cm ^{3 of} absolute ethanol and 1.15 g of metallic sodium. It is cooled and left for 30 minutes with stirring at room temperature. A solution of 12 ^ 2 g of phenyl-4-chloro-2-methyflutene- (2) -yl-sulfone in 50 cm ^{3 of} absolute ethanol is then introduced and the mixture is heated under reflux (78 ° C.) for 3 hours. The mixture is removed the alcohol in vacuo, the residue is taken up in 100 cm ^{3 of} water, extracted with ether and treated the ether layers as before, giving 10.8 g of a viscous product in which, by NMR spectrography, 40% of a product of the formula

15th

Example 9

A solution of 0.65 g of ethyl acetylacetate in 5 cm ^{3 of} tetrahydrofuran is added to 0315 g of potassium tert-butoxide in 5 cm ^{3 of tetrahydrofuran over the course of 2 minutes.} A solution of 1.34 g of 1- (2-methylbutadienylsulfonyl) -3,7-dimethyloctadiene- (2,6) in 10 cm ^{3 of} tetrahydrofuran is then introduced over the course of 3 minutes and then left for 1 hour and 40 minutes 25 ° C with stirring.

The reaction mass is poured into a mixture of 25 cm ^{3 of} water and 25 cm ^{3 of ethyl ether.} The aqueous layer is decanted and extracted twice with 20 cm ^{3 of} ethyl ether each time. A red oil containing 1.6 g of a product of the formula is isolated from the combined ether layers treated as above

25th

30th

35

C ₆ H ₅ -SO ₂ -CH ₂ -C (CH ₃ I = CH-CH ₂ -CH (COCH ₃ J ₂₎ identified and determined so,

COCH ₃ COOC ₂ H ₅

The degree of conversion is 100% and the yield is 80%.

The starting sulfinate was prepared by keeping a solution of 44 g of geranyl bromide in 30 cm ^{3 of} methanol and a solution of 34.7 g of potassium 2-methylbutadienyl sulfinate in 100 cm ^{3 of} dimethyl sulfoxide in contact at room temperature with stirring.

The potassium 2-methylbutadienyl sulfinate was through Reaction of potassium tert-butoxide with cyclic isoprene sulfone

t0964S / 308

Claims (1)

Patent claims: 1. Sulfones containing a methyl pentenyl chain the general form jl /
0-SO, -CH ₁ -CY = CY ₁ -CH, -CH (1)