DE2509576B2 - PROCESS FOR THE MANUFACTURING OF ALPHA, BETA-UNSATABLED GAMMA-LACTONE DERIVATIVES - Google Patents

Description

HO-C-Ce = C-C-OH

ί I

CH ₁ CH ₃

in which R ₁ and R _{2 have} the meaning given above, with an orthoacetic acid ester of the general formula

where Ri is an alkyl group having 1 to 4 carbon atoms, R _{2 is} an alkyl group having 1 to 4 carbon atoms OR ₄
R, - CH ₁ -C-OR ₅

'I.
OR,

(Uf)

in which R _{1 has} the meaning given above and R ₄ , R ₅ and R ₆ each represent an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, where R ₄ , Rs and R »can be identical or different , in the presence of a phenol, a fatty acid having 2 to 6 carbon atoms, an aromatic carboxylic acid, mineral acid or sulfonic acid as the acidic catalyst, which is used in an amount of 0.001 to 20% by weight, based on the weight of the starting compound (II) a temperature of approximately 100 to 25O ⁰ C converts.

So far, for the production of lactone derivatives, the lactone derivatives to be produced according to the invention have been used are similar, the following methods are known:

That described in Journal of the American Chemical Society, Vol. 89, pp. 3850-3857 (1967) The method is based on 2,4,6-tri-t-butyl-4-methoxy-2,5-cyclohexadienone, which is subjected to photolysis and wherein a variety of photolysis products are formed. From a certain such The product, a dicyclopentanone, is obtained by pyrolysis of various unsaturated lactones.

The disadvantages of this process are that the photolysis and the pyrolysis run inconsistently that it is expensive and the yield of the lactone is low.

According to a method described in the Journal of the American Chemical Society, Volume 94, pages 4395-4396 (1972), a similar lactone is prepared in a complicated multi-step process using expensive reagents such as n-BuLi and (CH ₂ = CH)? CuLi , manufactured. This method, too, therefore has considerable disadvantages.

According to the method according to the invention it is now possible in a very simple manner in one step from easily available starting materials the relevant

fio «, ^ - unsaturated γ-lactones in very good yields to divide.

The following are particularly suitable as starting compounds of the general formula (II):

(15 2,5-dimethyl-3-hexyne-2,5-diol,
3,6-dimethyl-4-octyne-3,6-diol,
2,4,7,9-tetramethyl-5-decyne-4,7-diol and
2,5,7-trimethyl-3-octyne-2,5-diol.

^2-f subs ituierte Orthoessigsäureesterverbindungen the general formula (III), the following compounds may be mentioned:

1,1,1-trimethoxyethane,

1,1,1-triethoxyethane,

1,1,1-tripropyloxyethane,

1,1,1 -Tricyclohexyloxyäthan,

1,1,1 -Tri- (n-butyloxy) -ethane,

1,1,1 -triethoxypropane,

1,1,1 -triethoxybutane,

1,1,1 -triethoxy pentane,

S-methyl-l.U-triethoxybutane,

2-cyclohexyl-l, 1,1 -trimethoxyethane,

l.l-dimethoxy-l-cyclohexyloxyethane and

1,1-dimethoxy · 1-pentoxyethane.

Suitable acidic catalysts are, for example, phenolic compounds such as
Phenol, o-, m- or p-nitrophenol,
o-, m- or p-cresol, o-, m- or p-xylenol,
2,6-dimethylphenol, 2,6-di-tert-butylphenol,
2,4,6-tri-sec-butylphenol,
2,4,6-tri-tert-butylphenol,
4-methyl-2,6-di-tert-butylphenol,
4-methyl-3,5-di-tert-butylphenol,
Hydroquinone, 2,5-di-tert-butylhydroquinone,
also lower fatty acids, for example acetic acid, propionic acid, butyric acid, isobutyric acid, cyclohexanecarboxylic acid, valeric acid, malonic acid, succinic acid,

2 S adipic acid and aromatic carboxylic acids such as benzoic acid, m-chlorobenzoic acid and sulfonic acids, such as benzenesulfonic acid, p-toluenesulfonic acid. Suitable Mineral acids are, for example, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid. To a It is particularly important to avoid dehydration of the diol of the formula (II) or other side reactions expedient to use phenols, aromatic carboxylic acids or fatty acids which have 2 to 6 carbon atoms contain. The amount of acidic catalyst used varies between 0.001 and 20% by weight and is preferably between 1 and 15% by weight, based on the weight of the starting compound (II).

A solvent is not necessary for carrying out the process according to the invention, but an inert solvent, for example
n-heptane, n-octane, toluene, o-,
m- or p-xylene, di-n-butyl ether,
tert-butanoI or N, N-dimethylformamide
be used.

The orthoacetic acid ester can be used in excess, so that it is used as a solvent at the same time serves.

The course of the reaction of the process according to the invention probably takes place in such a way that the Reaction via a ketene / acetal complex in one Transition state to a 6-membered ring and an ester of a hydroxyallene carboxylic acid as Intermediate connections proceed according to the following scheme:

[II] + [III]
H 7.1

R ₄ OH ₁ -R ₅ OH

-R ₆ OH [I]

OR ₆

R ₂ -C
HO CH ₃

OR ₆

C-C = C = C

/ I \

R ₄ OH CH ₃

As a result of dealcoholization in an equilibrium system, as shown in the above equation As can be seen, the alcohol formed as a by-product during the reaction becomes preferably continuous driven out of the reaction system.

These process products are suitable, for example, as intermediates for the synthesis of chrysanthemum monocarboxylic acids and their esters, which are insecticides, as well as for the synthesis of non-isoprenoid Terpene alcohols.

Of the compounds of general formula (I), the one in which R 1 and R ₂ denote the methyl group and R 3 denotes a hydrogen atom, denotes a, 3-dehydropyrocin and from which the pyrocin can easily be prepared by selective reduction of the α, 3 double bond can. The pyrocin has an insecticidal activity. From this compound, in turn, chrysanthemum monocarboxylic acid and non-isoprenoid terpene alcohols can be prepared (cf. W. Su crow, W. Richter, "Tetrahedron Letters 1970", No. 42, 3675 and M. Uchiyama, M. Matsui, "Agr. Biol . Chem. «, 26, No. 8,532 [1962]) ·

In the following examples, all parts refer to weight, unless otherwise is indicated, the NMR spectra are in carbon tetrachloride at 60 MHz and at room temperature measured using tetramethylsilane as an internal standard. In the case of the NMR values, means the symbol (s) a single «, (bs) a broad singlet, (t) a triplet, (m) a multiple and (J) a coupling constant.

example 1

At a reaction temperature between 140 and 150 ^° C., 14.2 parts of 2,5-dimethyl-3-hexyne-2,5-diol, 32.4 parts of triethyl orthoacetate and 1.4 parts of phenol are stirred together, the ethanol formed as a by-product is continuously distilled off. After 24 hours the reaction mixture is distilled directly under reduced pressure. The at Kp.

C = HL-C-
/ Il C.
η -C
I \ H ₃ CH ₃ CC Il
O O CH ₁
/ in a yield of 96%.
The connection has the following / Characteristics:

5 6

0.07 / 92 to 94 ° C passing fraction represents the parts of phenol are used «^ -Unsaturated y-lactone of the formula <x, j9-unsaturated y-lactone of the formula

H ₃ C LH ₃ ^H 3 ^C _V / ' ^Hl

C = HC-C C

/ Il l \

H ₃ C HC O CH ₁

'C! O

Il ο

The yield is 91%. This connection

has the following properties: 15

Bp 0.07:

Melting point: 82 to 84 ° C

62 to 62.5 ° C NMR spectrum (o.ppm):

Nuclear Magnetic Resonance Spectrum o (ppm): 1.36 (sh) 6 H; 1.66 (bs) 6H; 1.95 (bs) 3H; 5.66 (bs) 1H

142 (s) 6H, 2.00 (bs) 6H, 5.68 (bs) 2H IR spectrum (pure):

IR spectrum (Nujol): 1753 cm - '(> C = O)

1734cm-i (> C = O)

Example 5

Example 2 The procedure described in Example 1 is

A mixture of 14.2 parts of 2,5-dimethyl-3-hexyn-25 is repeated, but with 2.1 parts of 2,5,9-trimethyldesa-2,5-diol and 32.4 parts of triethyl orthoacetate with 1.4 8-en-3-yn-2,5-diol, 3.2 parts of triethyl orthoacetate and 0.1 part of isobutyric acid were added in small portions. The parts isobutyric acid are used. This gives the mixture with constant stirring 12 hours x <, /? - y-lactone of the formula 130 to 14O ⁰ C heated unsaturated The by-product

Ethanol is continuously extracted from the reaction sy- 30 H ₃ C CH,

star expelled. The reaction mixture obtained ^Χ ρ ₌ μρ_ ₍ p ⁷ ru

is then directly as described in example 1 under / ΙΪ ^{N /} *

distilled off under reduced pressure. This is obtained in H ₃ C Jl _Q CH ₂ -CH ₂ -CH = C

Example 1 given Λ, / 3-unsaturated γ-lactone in \ / ^ H

a yield of 81%. 35 ^ "^ ³

Example 3 Il

The procedure described in Example 1 is

repeated, but 10 parts of 3,6-dimethyl-4-octyne- in a yield of 76%.

3,6-diol, 19.0 parts of triethyl orthoacetate and 1.0 part of 40 The compound has the following properties: Phenol can be used. The «, ^ - unsaturated γ -lactone of the formula 92Ws 96 ° C. is obtained

H ₃ C CH ₃ IR spectrum (pure):

\ / 1745cm - '(> C = O)

C = HC-C C NMR spectrum (<5 ppm):

/ II | \ 1.42 (s, 3H), 1.65 (m, 6H), 1.98 (m, 6H), 5.0

H ₅ C ₂ HC OC ₂ H ₅ methyl signals:

\ / 5.05 (m, 1H), 5.65 (m, 1H), 5.80 (1H) _Cn olefinic signals.

Il

O Example 6

in a yield of 95%. The procedure described in Example 1 is

The compound has the following properties: repeated, but 5.5 parts of 2,5-dimethyl-3-no-

55 nin-2,5-diol, 9.7 parts of triethyl orthoacetate and 0.3 parts

ins w \ nvr isobutyric acid are used. One obtains the α,

κ, Λο ο ι , χ ^ ^ -unsaturated y-lactone of the formula

Nuclear Magnetic Resonance Spectrum (ό, ppm): r e>'

0.74 (t, J = 7cps) 3H; l, ll (t, J = 7cps) 3H; H ₃ CC ₄ H ₉

1.5-1.9 (m) 2H, 1.98 (s) 3H; 2.0-2.4 (m) 2H; 5.70 (bs) \ /

IR spectrum (pure): / || | \

1745cm - '(> C = O) H ₃ C HC O CH ₃

\ / B eis ρ ie 1 4 ₆ C

The procedure described in Example 1 is ^

repeated, but with 4.8 parts of 2,5-dimethyl-3-he- °

xyne-2,5-diol, 12.0 parts of triethyl orthopropionate and 0.5 in a yield of 60%.

he

^ 25

09

The connection has the following properties:

Bp 0.2:

103 to 108 ⁰ C IR spectrum (pure):

1745cm - '(> C == O) NMR spectrum (ό ppm):

1.99 (m, 6H) methyl signal; 5.66 (m, 1H),

5.80 (s, l H) olefinic signals.

Examples 7 to 12

identical to that of example 1. The respective yields can be found in Table I:

Table 1

Example acid catalyst

Yield to

», / (- unsaturated

y-Laeton

The procedure described in Example 1 is repeated with the exception that the compounds given in Table 1 below are used as the acid catalyst instead of phenol. The α, β-unsaturated _{γ-lactone obtained lsl m} j _t

Cyclohexanecarboxylic acid 95

Adipic acid 91

Benzoic acid 87

p-Toluenesulfonic Acid 65

Phosphoric acid 62

Hydroquinone 93

Claims (1)

Claim: Process for the production of «, ^ - unsaturated y-lactone derivatives of the general one formula R, C = CH CH, C- Il c R ₂ C-CH, I. ο wherein Ri is an alkyl group having 1 to 4 carbon atoms, R2 is an alkyl group with 1 to 4 carbon atoms or an alkylene group with 2 to 20 Represents carbon atoms and R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms represents, characterized in that a 2-alkyne-1,4-diol of the general formula R ₁ R ₂ H ₀ -CC = CC-OH (ID CH ₃ CH ₃ in which R ₁ and R _{2 have} the meaning given above, with an orthoacetic acid ester of the general formula OR ₄
R ₃ -CH ₂ -C-OR ₅ OR ₆ (III) in which R _{3 has} the meaning given above and R ₄ , R5 and Rt each represent an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, where R4, R5 and R6 can be the same or different, in the presence of a phenol , a fatty acid having 2 to 6 carbon atoms, an aromatic carboxylic acid, mineral acid or sulfonic acid as the acidic catalyst, which is used in an amount of 0.001 to 20% by weight, based on the weight of the starting compound (II), at a temperature of about 100 to 25O ⁰ C converts. The invention relates to a process for the preparation of γ-unsaturated γ-lactone derivatives of the general formula R, C = CH-C- CH, R ₂ C-CH ₃
O or an alkenyl group with 2 to 20 carbon atoms and R _{1 represents} a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, which is characterized in that a 2-alkyne-1,4-diol of the general formula