JPS5818395A - Novel organic germanium compound and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formula (X is halogen; R is H or 1-3C alkyl). EXAMPLE:beta-Trichlorogermylpropionaldehyde. USE:Intermediate of an organic geramanium sesquioxide having physiological activities such as macrophage activator, interferon inducer, etc. PROCESS:The compound of formula can be prepared by reacting the halogermanium hydride of formula X3 GeH (e.g.trichlorogernanium hydride) with an aldehyde compound of formula CH2=CR-CHO (e.g. acrolein) in a solvent such as diethyl ether. The compound can be converted to an organic germanium sesquioxide by oxidizing with molecular oxygen, and hydrolyzing the product.

Description

[Detailed description of the invention]

The present invention relates to a new 31t germanium oxide compound and a method for producing the same. More specifically, this article relates to a novel germanium that has unique physiological activity and is valuable as an intermediate for organic germanium sesquioxides, and a method for producing the same. In recent years, organic germanium compounds, such as germanium sesquioxide [(C7e-C1x -CH, -C
00N-containing Or'1 has the value jQ property ℃yY fat-soluble and lipophilic amphoteric property, and its unique J

[
It is attracting attention because of its physiological activity. This I' IA germanium sesquioxide is used as its cow life se1.
] Contains 7-diactivator, interferon inducer, etc., and is an anticancer agent. 'Suppression of allergic effects, hypertension, and lung cramps! j
. It is a compound that has been attracting attention in recent years as a substance that is said to have medicinal effects on bronchial llili, breathing, suppressing morning sickness, nausea, and diuresis. The present invention provides (Ge -CH2-CH2-C0OH)2o,
This invention relates to novel germanium compounds that are useful intermediates for obtaining. Conventionally, as an intermediate for the organogermanium sesquioxide described above, for example, (1) a compound such as C4c e CHt Cut CN described in JP-A-46-2498, (2) a compound described in JP-A-55-81890; Compounds such as Compound (2) requires methyl acrylate as a raw material, and since the product is solid, it is difficult to purify it by simple means such as distillation. The odor is a problem when handling, and methanol is generated when converted to organic germane sesquioxide, which is troublesome to process and recover. We have arrived at the present invention as a result of repeated research on new organic germanium compounds free of defects and methods for producing the same.In short, the present invention is based on the following general formula (I) -X3Ge -CM, -CH-CH2 It is a novel organogermanium compound represented by --.
(,-Cl-C)To (where R is a hydrogen atom: &
2 represents an alkyl group having 1 to 3 carbon atoms).
However, the definitions of X and R in the formula are the same as in ++U. The organic germanium compound represented by the general formula (1) according to the present invention can be distilled and easily separated as a pure tr compound, and can be oxidized with molecular oxygen and hydrolyzed, for example. , 1 "It is an industrially extremely valuable compound because it can be easily converted into the useful organic germanium sesquioxide mentioned in 1. According to the research 1c of the present inventors, the compound represented by the above formula (1) The organic germanium compound represented by the general formula X3Ge)T (
i,'! , L X indicates a halogen atom) is represented by the general formula 〇H,=
It has been found that it can be easily produced by reacting with an aldehyde compound represented by CR-CHO (where R represents a hydrogen atom or a furkyl group having 1 to 3 carbon atoms). In the general formula (I) of the present invention and X, GeHIc represents a halogen atom, and a chlorine atom or a bromine atom is particularly preferred. Furthermore, R in the general formula (1) and the general formula CH,=CHR-CHO represents a hydrogen atom or a furkyl group having 1 to 3 carbon atoms, and preferred examples of this alkyl group include a methyl group, a Examples include the pyl group and the p-pvir group. m
959), a method by the reaction of metal germanium with a hydrogen halide such as chlorine gas, or a process involving the reaction of metal germanium with a hydrogen halide such as chlorine gas, or as described in 959). <
It can be produced by the method of reacting tetrahalogermanium with molecular hydrogen under a highly humid phase to obtain trinologermanicum hydride, as described in 2. 1111 C1 (t = CR-CHO aldehyde compounds can be easily prepared by vapor phase butylation of the formula CH2 = CR-CH, for example). - When p-germanization-hydra ide and aldehyde compound are reacted 6-, this reaction can be carried out without a solvent, but it is preferable to use a solvent. In this case, the solvent is preferably one that is inert and liquid under reaction conditions that do not adversely affect the reaction, such as alcohol, alcohol, carbon, hydrocarbon, halogenated hydrocarbon, and organic carboxylic acid. Examples of such solvents include methanol. Ethanol, furopanol, 7setone, ethyl ether, propyl ether, tetrahydrofuran, carbon tetrachloride, chloroform, etc. are preferred. By using such a solvent, it is possible to obtain one of the key points of the chemical theory. Reaction V, rnr may be carried out at, for example, θ°C, preferably at a temperature higher than room temperature, On the other hand, it is better to avoid temperatures above 200°C because the I11 reaction occurs.
is isolated by distillation, acidified with molecular oxygen, and then hydrolyzed to produce physiologically active organic germanium sesquioxides (Ge -CH, -CH,
-C0OH), giving 03. V) The present invention will be described in detail with reference to Examples. Example 1 (Synthesis of trichlorogermanium high F phyto°) Internal diameter] 0. A quartz T (iφ×250 mm in length) was packed with quartz wool, and the temperature inside the tube was raised to 900°C. A mixture of H, gas, and germanium tetrachloride was supplied to this, and the reaction liquid was collected in a dry ice-methanol trap. After the reaction is complete, heat the trap at 60 to 70°C to perform single evaporation and transfer the dough to another trap for purification.aJt1
A transparent liquid is produced. The boiling point of this thing is 75"C
Met. Example 2 (Synthesis of β-triclop gelmyl 7'p pionaldehyde) Contents: 50 cc of Fukusco ethyl ether 25 m
Prepare Cls G while cooling on ice from outside 11i+.
Add eTT7, 8.9. While stirring, 243 g of 1 g was added dropwise over 5 minutes. React for 2 hr at room temperature. After that, the ether was expelled and the desired compound 9.7.9 was obtained by vacuum distillation (boiling point 69-70℃/2
yxvH & ). Infrared absorption spectrum of the compound, N
The MR and mass spectrometry data are as follows. 1, R: 2720Crn, 1700>, 8]
0ci-'NMR: δ2.24(2H), δ3.00(
2H). δ9.80 (IH) Mass: M+236 (c/-3s, Ge-
74) Condolences person: Sokujin patent attorney representing Teijin Limited 1) Jun Hiroshi 9-

Claims (1)

[Scope of Claims] 1. A novel organic germanium compound represented by the following general formula (1) % formula % (), 2. Represented by the general formula X, GeH (where X represents a \ρ gene atom)ノ＼ρgurmaniwamuno-idride general formula CH,
= CR-CHO (However, R hydrogen atom or carbon number 1~
3 of 7 notes/1. The following general formula (
I) ■ XsG e CHt -CH-CHO-- (I)
A method for producing a novel organogermanium compound represented by (wherein X and Rσ-) are defined as in Section 1111.