DE1957312C3 - Process for the preparation of 4,5,6,7-tetrahydro-cyclopenta-13-dioxinonen- (4) - Google Patents

Description

in the

R and R ¹ stand for the radicals indicated above

in an inert organic solvent at temperatures between -20 and + 80 ° C below Addition of a tertiary amine implemented as an acid binder.

Xylene, which also contain mercury (H) chloride and preheated to 130 "to 140" C. Solutions from 2-Diazo-dihydroresorcinol in xylene is added dropwise

However, the known method has a number of disadvantages. The production of the diazo compound required for thermolysis is very expensive. In addition, the reactions proceed only in the presence of mercuric salts and require high temperatures, the tetrahydro-cyclopenta-13 dioxinone- (4) for this comparison _C drive precludes synthesis of thermolabile

A process has now been found which enables ^, ej-Tetrahydro-cyclopenta-l ^ -dioxInone- (4) in a simple manner and without the disadvantages of the known procedure.

The process according to the invention for the preparation of 4,5,6,7-tetrahydro-cyclopenta-1,3-dioxinonen- (4) the general formula

R ³ R ² O

N Ii

R ⁴ 'V ^ O

-Χ '1 Uri ⁵ V ° Ί

A κ

R "R ⁷

(I)

in the

R and R ^{1 represent} a hydrogen atom, an alkyl haloalkyl-. Alkenyl, aralkyl or aralkenyl radicals each with up to 6 carbon atoms in the alk (en) yl part, a cycloalkyl radical with 5 to 6 carbon atoms, which is optionally replaced by a lower alkyl, lower alkoxy, lower alkyl mercapto, lower alkyl sulfoxy, lower alkyl sulfonyl Radical, a halogen atom or the amino, nitro or cyano group-substituted phenyl radical or a furyl radical, or in the

R and R ¹ together represent the cyclohexyl radical and

R ² to R ^{7 represent} a hydrogen atom or an alkyl radical with up to 6 carbon atoms,

is characterized in that a dicarboxylic acid dihalide is used the general formula

R ² R ⁴ R "O

XC (H, C CCC ^- X (II)

"III

W R ⁵ R ⁷

in the

R ² to R ^{7 has} the meaning given above and

X represents a chlorine or bromine atom, with an aldehyde or ketone of the general formula

R ¹

O C

(HI)

It is already known (see. Chemical reports, Volume 98, pages 2099-2102 [1965]) that one in the 2-position substituted 4,5,6,7-tetrahydro-cyclopenta-U-dioxinone- (4) obtained when one approaches solutions of aldehydes in

in the

R and R ¹ stand for the radicals given above,

in an inert organic solvent at temperatures between -20 and + 8O ⁰ C with the addition of a tertiary amine as an acid binder.

It is extremely surprising that after the process according to the invention from the two open-chain Reaction components in a 1-stage reaction the acyclic tetrahydrocyclopental, 3-dioxinone- (4) in question can be obtained in good yields and high purity.

The process according to the invention has great advantages over the diazoketone method. It enables the compounds of general formula (I) to be prepared from readily available starting materials and under mild reaction conditions in good yields and high purity. The low reaction temperatures are particularly advantageous for the preparation of the thermally labile 2-alkyl- or 2,2-dialkyl-4A6,7-tetrahydro-cyclopenta-1,3-dioxino-, _s ne- (4), which are known after the above-mentioned Method cannot be produced.

The starting materials of the general formula (H) are preferably those in which R ² to R ^{7 represent} a hydrogen atom or an alkyl radical having 1 to 3 carbon atoms. The starting compounds can in a known manner, for. B. by reacting a corresponding dicarboxylic acid with thionyl chloride, such as adipic acid dichloride, 2,2-dimethyladipic acid dichloride, 2,2,4-trimethyladipic acid dichloride.

Preferred aldehydes or ketones which are used as starting materials are, for. B. those in which in the general formula (III) R and R ¹ denote a hydrogen atom, an alkyl, haloalkyl or alkenyl radical with ^ u up to 4 carbon atoms, or the phenylmethyl, phenylethenyl or phenyl Represent radicals which are preferably optionally substituted by the methyl, isopropyl, methoxy, ethoxy, methylmercapto, methylsulfoxy, methylsulfonyl, nitro group or a fluorine or chlorine atom. The aldehydes and ketones to be used as starting materials are known and can be obtained according to generally known preparation procedures.

Suitable aldehydes and ketones are, for. B .:

Formaldehyde, acetaldehyde, chloroacetaldehyde,
Trichloroacetaldehyde, propionaldehyde, butyraldehyde,
Acrolein, benzaldehyde, 4-methylbenzaldehyde,
4- fluorobenzaldehyde, 4-chlorobenzaldehyde,
2-methylbenzaldehyde, 2-chlorobenzaldehyde, 4-nitrobenzaldehyde, anisaldehyde,
4-methylmercapto-benzaldehyde,
4-methylsulfonylbenzaldehyde, cinnamaldehyde,
Phenylacetaldehyde, acetone, methyl ethyl ketone,
Diethyl ketone, dichloroacetone, acetophenone, cyclohexanone, furfural.

Both non-polar and polar organic solvents can be used as diluents for example aliphatic and aromatic hydrocarbons such as hexane and benzene. Ether how Diethyl ether, dioxane and tetrahydrofuran, and halogenated hydrocarbons such as dichloromethane and carbon tetrachloride.

As a tertiary amine for acid binding z. B. Trimethylamine, triethylamine or pyridine. Triethylamine is preferred.

The reaction is carried out at temperatures between -20 and + 8O ⁰ C, preferably between 0 and 40 ° C. When carrying out the process according to the invention, the diacid halide and the carbonyl component are used in the presence of the calculated amount of the tertiary amine in a molar ratio of 1: 1 to 1: 4, preferably in a molar ratio of 1: 2 such, or dissolved, added dropwise in one of the abovementioned diluents to the solution of the dicarboxylic acid halide and the carbonyl component under stirring and the reaction mixture optionally cooled. in the work up is first filtered to remove the precipitated ammonium salt, and the filtrate concentrated in vacuo at bath temperatures of 20 to 8O ⁰ C, preferably at 20 to 30 ° C., concentrated or evaporated and the product that remains is purified by the customary methods.

Some of the compounds obtainable by the process according to the invention are known (cf. in this regard Chemical Reports, Volume 98, Pages 2099-2102 [19651).

The products of the process are intermediate products. For example, they can be used to pass through Reaction with aniline or its derivatives to produce compounds with opening of the dioxinone ring, which have a fungicidal activity against phytopathogenic fungi.

example 1
O

cn,

A solution of 80.8 g (0.8 mol) of triethylamine is added dropwise with stirring to a solution of 73.2 g (0.4 mol) of adipic acid dichloride and 69.6 g (1.2 mol) of acetone in 700 ml of dry ether in 50 ml of ether so quickly that the reaction mixture just boils. After completion of the amine addition, the mixture is stirred for one hour at room temperature, the triethylammonium chloride is filtered off, washed twice with 50 ml of dry ether and the filtrate claimed in vacuo at a bath temperature of 20 to 30 ⁰ C evaporated. The residue is taken up in about 100 ml of ether, a little activated charcoal is added, the mixture is heated to the boil and filtered. By cooling the filtrate to -40 to -50 ° C, 48.3 g of I '^ - dimethyl ^ Aey-tetrahydrocyclopenta-1,3-dioxinone- (4) are obtained in the form of colorless crystals with a melting point of 36 to 38 ° C Yield: 71.5% of theory.

Example 2
O

Λ Ο

O-X

cn., cn.,

VlI.,

In a solution of 42.4 g (0.2 mol) of 2,2-dimethyladipic acid dichloride and 34.8 g (0.6 mol) of acetone in 600 ml of ether are 40.4 g (0.4 mol) within 45 minutes Triethylamine was added dropwise. After the amine hydrochloride has been filtered off with suction, the solvent is reduced in vacuo drawn off and the residue recrystallized from ether. 33.5 g of 2,2,7,7-tetramethyl ^ .S.ey-tetrahydro-cyclopenta-1,3-dioxinone- (4) are obtained from 64 to 65 ° C. Yield: 85.4% of theory.

In an analogous manner, using the corresponding reaction components instead of the The starting materials given above receive the following compounds:

Example I nimel

! Musical I-.iüenscluinen

Howl in 'theory

C ₂ H ₅

P CH ₃

C ₂ H ₅

O CH,

O H

O H

O H

CH,

IR spectrum:
Absorption at 1735
and 1635 cm " ¹

F. 32 35 C

IR spectrum:
Absorption at 1720
and 1640 cm ' ¹

F. 93 95 C

F. 97 C

F. 87-88 "C

F. 101-103 "C

F. 92-93 "C

F. 109-111 "C

88.5

71.2

51.5

8.4

71.3

59

61.5

71.5

40

Forlscizurm

Example formula

/ \ Λθ H

CH ₃ CH ₃ H ₃ C

CH ₃ CH ₃ O

CH = CH

/OH

I / Physical characteristics

M.p. 104-105 "C

M.p. 85-86C

M.p. 71-73 "C

M.p. 105-107 = C

M.p. 115-118-C

Mp. 129-130 ⁰ C

Ausl der '

Claims (1)

Claim: Process for the preparation of 4,5,6,7-tetrahydrocyclopenta-l _r 3-dioxinonen- (4) of the general formula R "R in the R and R ^{1 are} hydrogen, alkyl, haloalkyl. Alkenyl, aralkyl or aralkenyl radicals each with up to 6 carbon atoms in the alk (en) yl part, a cycloalkyl radical with 5 to 6 carbon atoms, which is optionally replaced by a lower alkyl, lower alkoxy, lower alkyl mercapto, lower alkyl sulfoxy, Lower alkylsulfonyl radical, a halogen atom or the amino, nitro or " Cyano group-substituted phenyl radical or a furyl radical, or in the R and R ¹ together represent the cyclohexyl radical and R- 'to R' represent a hydrogen atom or an alkyl radical with up to 6 carbon atoms mean characterized in that a dicarboxylic acid dihalide of the general formula R ² R ⁴ R "O X C CH, C C C CX R · ¹ R ⁵ R ⁷ in the R ² to R 'has the abovementioned meaning and
X represents a chlorine or bromine atom, with an aldehyde or ketone of the general formula O C R ¹