JPS58103384A - Derivatives of cyano-substituted ketones and aldehydes as novel composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cyano-substituted ketone and aldehyde derivatives as novel compositions.

Soviet Union Patent No. 56 published October 12, 1977
No. 9,575 discloses 2-cyano-substituted dioxolane compounds. Furthermore, ring-substituted derivatives are not mentioned. The above compounds are reported to be used as fillers in piteumene lacquer components for electrical insulation.

Fisher and Smith J, Org, Chum, 2
5.319-324 (1960) to 2-vinyl-4-
Hydroxymethyl-1,3-dioxolane and 2-(
2-cyanoethyl)-4,4,6-)trimethyl-1,
The production of 3-dioxane has been announced.

No derivatives with hydroxy or hydroxyalkyl substituents or derivatives thereof in addition to cyanoalkyl substituents have been produced.

The present invention relates to a carbon compound of the formula: LAB represents a monovalent group having 1 to 1 O1 atoms, and represents branched or linear alkylene and -CCH,
)-E-OCII2CHCR□)9 (However, Ro is hydrogen,
2 to 10 carbon atoms selected from the group consisting of methyl or ethyl, where n is 1 or an integer of 2 or more
(Represents a divalent group having iH, R' is hydrogen ↓ and C9H2,
(R□ shall be as defined above)
LAR# represents hydrogen or X and 8 represents zero or lt-. However, if - is zero, at least 1 R' is not hydrogen, or 8 is 1
``C is a compound represented by at least one OR' or R'' which is not hydrogen.

These compounds are used in hydraulic fluids (hydrtmlic fhb).
It is particularly suitable for use as a component for functional fluids such as ids) and heat transfer fluids.

The novel 1,3-dioxane and dioxolane derivatives of the present invention are conveniently prepared by reaction of a polyhydroxyl compound with a reactive cyano-substituted compound of formula t corresponding to the desired cyclic compound. Specifically, it represents a monovalent group having a carbon number of 1 to 10' selected from reactive cyano-substituted or branched or linear alkyl and its cyano-1 or hydroxy-substituted derivative groups, and R3 is C
1-4 alkyl) may also be included. It is preferable that R2 is hydrogen or methyl and B is C2-60 straight chain or branched alkylene.

The polyhydroxyl compounds used in the preparation of the compounds of the present invention are di, 2- or 1,3-dihydroxy-substituted aliphatic compounds further substituted with hydroxyalkyl substituents or derivatives thereof. Suitable derivatives of hydroxyalkyl substituents are those produced by reaction of a hydroxy moiety with conventional reactive substances capable of displacing its hydrogen. Included are substituents in which hydroxy is substituted with alkoxy, aralkoxy, acyloxy, or organosiloxy, and (poly)alkylene oxide-based ether derivatives having terminals of the above alkoxy, aralkoxy, hydroxyalkoxy, acyloxy, or organosiloxy substituents. These compounds and methods for their preparation are well known in the art and correspond to either of the following two formulas: R' and R# in the above formula are 9 as defined above, or at least one of R' or R'' is not hydrogen.

A more preferably used Borich-Droxyl compound is glycerin, which is a preferred polyhydroxyl reactant that is widely commercially available and readily available.

The following polyhydroxyl compounds may be suitable for use in preparing the compounds of this invention: Glycerin: 1.2.4-) Lyhydroxyptane: 1.2.4-)
Lihydroxybentane; 1.2.5-) Lihydroxypentane; 1.2-dihydroxy-3-(2-hydroxyethoxy) pronokun; 1.2-dihydroxy-3-(
1.2-dihydroxy-3-[hydroxy(poly)alkyleneoxy]propanes, e.g. 1,2-dihydroxy-3-[hydroxydi(ethyleneoxy)]propane, 1.2 -dihydroxy-3-[hydroxydi(propyleneoxy)]propane, 1,2-dihydroxy-3-(hydroxyethyleneoxypropyleneoxy)propane; 1,2-dihydroxy-3-fluexypropanes,
For example, 1,2-dihydroxy-3-methoxypropane, 1,2-dihydroxy-3-t-butoxypropane,
1.2--/Hydroxy-3-age-butoxypropane: 1.2-dihydroxy-3-[alkoxy(poly)alkyleneoxy]propanes, e.g. 1,2-dihydroxy-3-[methoxydi(ethyleneoxy)]propane , 1,2-dihydroxy-3-[ethoxydi(propyleneoxy)]propane, 1,2-dihydroxy-3-[ptoxydi(ethyleneoxy)propoxy]propane: 1,2-dihydroxy-3-acyloxypropanes, e.g. 1,2-Dihydro axy-3-(acetyloxy)propane/s1,2-dihydroxy-3-(propionyloxy)propane; 1,2-dihydroxy-3-[acyloxy(poly)alkyleneoxy]propanes , for example 1,2-dihydroxy-3-(acetyloxyethoxy)propane, 1,2-dihydroxy-3-(acetyloxyethyleneoxypropyleneoxy)propane, 1,2-dihydroxy-3-[benzoyloxy(ethyleneoxy) ] Propane; 1,2-dihydroxy-3-organosiloxypropanes, such as 1,2-dihydroxy-3-'()-limethylsiloxy) propane and 1,2-dihydroxy-3-(
Trimethoxysiloxy)propane: 1,2-dihydroxy-3-[organosiloxy(poly)alkyleneoxy]propanes, such as 1,2-dihydroxy-3-[()riethersiloxy)
ethyleneoxypropyleneoxy]propane, 1,2-dihydroxy-3-(()riphenylsiloxy)di(ethyleneoxy)copropane, 1,2-dihydroxy)"o-'I-cy3-[()rimethoxysiloxy ))9(1-terenoxy)]propane: 1,3-dihydroxy substituted compounds, e.g. 1.3.
5-trihydroxypentane, 1,3-dihydroxy-
2-methoxypropane, 1,3-dihydroxy-2-(
2-hydroxyethoxy) prohas 1,3-dihydroxy-2-(2-methoxyethoxy)butane, 1,3-dihydroxy-2-(2-hydroxyethoxycobutane,
1.3-dihydroxy-4-(2-methoxyethoxy)
ButaA1.3-dihydroxy-4-(hydroxyethyleneoxypropyleneoxy)butane, 1,3-dihydroxy-5-[()rimethoxysiloxy)di(propyleneoxy)]pentane.

The reaction may preferably be carried out in the presence of a catalytically effective amount of an acidic catalyst such as a sulfonic acid, sulfonic acid resin or other strong acid or strong acid resin which suitably catalyzes this type of reaction. The molar ratio of catalyst to reactive cyano-substituted reactant is approximately 0.
0001/1.0 to about 0.1/1.0, preferably about 0.001/1.0 to about 0.05/1.0.

It is convenient to carry out the reaction in a solvent, preferably one that readily forms an azeotrope with water or lower alkanols and allows rapid removal of water or lower alkanol by-products formed during the reaction. Furthermore, it is preferable that no azeotrope is formed with any of the reactants. Examples of suitable solvents include benzene, toluene, petroleum ether, and chlorinated aliphatic solvents.

The reaction can also be carried out without a solvent. In this case, the water or lower alkanol produced during the reaction can be removed by direct distillation, preferably at a temperature and reduced pressure that prevents the formation of oligomers that may form at elevated temperatures.

The reaction is carried out at temperatures from about 0°C to about 200°C depending on the reactants used, pressure and other operating conditions.

The required reaction time will vary depending on the reactants used and operating conditions. Generally, reaction times of from about 1 to about 48 hours are sufficient to convert substantially all of the starting materials used for a given amount.

Large excesses of either reactant can be used. The molar ratio of cyano-substituted reactant to polyhydroxyl compound is approximately 20
/1 to about 1/20. To avoid separation of large amounts of unreacted compounds, the reactants may be mixed in approximately equimolar ratios, such as in a molar ratio range of about 1 to about 1 part. The best ratio is about 1.2/1.0 to about 1.0/1°2. An excess of the lower boiling reactant is used over either the polyhydroxyl compound or the cyano-substituted reactant to achieve substantially complete reaction of the higher boiling reactant. This process simplifies subsequent distillative separation of the cyclic products from the reactants by creating a mixture of components with maximum differences in boiling points.

It is, of course, also appropriate to add nitrile substituents to the previously formed and subsequently substituted compounds in order to form all the desired substituted compounds.

Thus, a compound having terminal ethylenic unsaturation at position 9 of the cyano substituent, but otherwise identical to the reactive carbonyl- or dialkyl-containing compounds described above, can be reacted with one of the polyhydroxyl compounds described above. Contact of a cyclic reaction product with an unsaturated alkyl substituent with hydrogen chloride results in the formation of the corresponding chloroalkyl-substituted cyclic compound, which can then be reacted with sodium cyanide to form the desired product. This alternative method is further described in Example 3.

In some cases the reaction produces a product mixture. For example, glycerin has three reactive hydroxyl substituents in close proximity, so the corresponding 1,3-dioxolane and 1,3-
Both dioxane derivatives are produced. If necessary, this product mixture can be separated by careful fractional distillation.

Yet another method for preparing the above compounds in which X is not hydrogen is to first form the desired cyanoalkyl-substituted cyclic compound and then displace the hydroxy or hahydroxyalkyl substituent. The hydrogen of this reactive hydroxy-containing substituent is replaced by X, which is part of a reactive substance capable of displacing hydrogen by known methods.

For example, alkoxy and aralkoxy moieties can be substituted for hydroxy using the Williamson synthesis method. Similarly, reactions with alkylene oxides, glycidyl ethers, or mixtures thereof can be used to form ether-functional phonogenic hydroxyl substituted alkoxy or polyalkyleneoxy substituents. Additionally, substituents may include, for example, acyloxy moieties formed by condensation of a hydroxyl-substituted cyclic compound with an acid halide such as acetyl chloride, and condensation of a hydroxyl-substituted cyclic compound with a halo-substituted organosilane, such as trimethylchlorosilane or trimethoxychlorosilane. It is the following organosiloxy moieties. By the same method dialkoxy, organosiloxy and acyloxy functional groups can be introduced into the substituent R by functionalization of the hydroxyl moiety of R2. Organosiloxy is a well-known lower alkyl
or phenyl-substituted siloxy group and lower alkoxy-
or phenoxy-substituted siloxy groups.

The following example deals with 8 At-cases of the present invention.

Example 1 In a 1000d round bottom flask, 5-oxohexanenitrile (3759, 3.4 mol), glycerin (248f
, 2.7 mol), p-toluenesulfonic acid (0, s
t, 0.0027 morn and toluene (200s
d, solvent) was added and heated under reflux. The azeotropic outflow water is collected and removed by the Dean-Stark device. Within 24 hours, 421 ml of R20 was collected and gas chromatographic analysis showed that 84 g of glycerin had been converted. Added 461 glycerin (0.5 mol, total 3.2 mol) to the disaster. After 48 hours, 58 m of R20 was collected, indicating that 98.7- of the glycerin had been converted. The liquid was cooled to 60°C, made alkaline with NaHCOa, and filtered. Solvent toluene and unreacted 5-oxynehexenenitrile t
- 15-plate Alderschau column (20- and 10-edit respectively) was removed by vacuum distillation. The product is mostly 2-methyl-2-(3-cyanopropyl)-4-
6J of hydroxymethyl-1,3-dioxolane, which was distilled to give a clear colorless liquid (boiling point 7■Hf, 171
．． 5℃). All samples with a purity of 997% or higher were mixed to give a final product of 98.5% purity. The separation yield was 75 cm.

Example 2 4,4-dimethoxybutanenitrile 8 in a 20-flask
A mixture of 19f and glycerin 584f was made into AI with methanesulfonic acid (3.2t) and stirred at 20C to make it homogeneous. The mixture was heated to about 56° C. under vacuum (about I Torr) to remove the methanol. Heating was continued until no methanol was produced (about 1 hour).

Triethylamine (7,6F)' was added to the solution to completely neutralize the acid, and the reaction mixture was vacuum distilled. Boiling point 117-137℃
A fractionated product of (0,1 Torr) was obtained. Vapor phase chromatographic analysis, nuclear magnetic resonance spectroscopy and infrared spectroscopy indicate that the product is 2-(2-cyanoethyl)-4-
Hydroxymethyl-1,3-dioxolane and 2-(
2-cyanoethyl)-5-hydroxy-1,3-dioxane. Total distillation yield is 9
It was 38f.

Example 3 A solution of about 3682 glycerin in chloroform was cooled to 14 DEG C. and bubbled into anhydrous chloride water. Add acrolein 1 while stirring above the liquid while maintaining a slight pressure.
9 drops of 68 f'i were added over 90 minutes. Addition of hydrogen chloride was continued for an additional hour while maintaining the temperature at -10°C or lower.

When the reaction mixture is brought back to temperature, it is covered with a suspension and left to stand.
Separated into layers. The lower layer containing the glycerin reaction product is
It was neutralized with about 300ml of triethylamine and washed with about 300ml of saturated sodium carbonate solution. The organic layer was separated again, dried over calcium sulfate, and heated under vacuum to remove residual acrolein and chloroform. By final vacuum distillation, 2-(
2-chloroethyl)-4-hydroxymethyl-1,3-
A mixture of dioxolane and 2-(2-chloroethyl)-5-hydroxy-1,3-dioxane was obtained.

A portion of the mixture was mixed with an equimolar amount of sodium cyanide in ethylene glycol monoethyl ether. The mixture was refluxed at 25°C for about 8 hours. Cool the mixture and add salt tF
Separated. Liquid F was distilled under vacuum to obtain a transparent BA light-colored liquid, which was determined by GC-mass spectrometry and nuclear magnetic resonance spectroscopy.
(2-cyanoethyl)-4-hydroxymethyl-1,3
-dioxolane and 2-(2-cyanoethyl)-5-hydroxy-1,3-dioxane.

Example 4-)! j Methylsilane derivative Acetal mixture 116F produced in Example 2, acid acceptor pyridine 7
To a solution of 9f and 454f of diethyl ether solvent was added dropwise 109f of trimethylchlorosilane with stirring. The temperature was maintained at 20-25°C with a water bath. Trimethylchlorosilane was added over t-1 hour. After stirring for an additional 30 minutes, the reaction mixture was cooled to about -10 DEG C. and the pyridine hydrochloride tp produced during the reaction was separated. The solution was washed twice with water from solution F t-1oo-, and the ether was removed in vacuo.

The product mixture was distilled in a 2.5m x 20a* distillation column to obtain a product 14 with a boiling point of 95-98°C (0.5 Torr) f.
0.3ft. Product #'12-(2-cyanoethyl)-4-()rimethersiloxymethyl)-1,3-dioxolane and 2-(2-cyanoethyl)-5-(trimethylsiloxy)-1,3-dioxane mixture Met.

Example 5. -7 Cetate Crocodile Conductor A mixture of 3.8 f acetyl chloride and triethylamine acid acceptor 5, Of was mixed at room temperature with vigorous stirring in a mixture of 5.42 g of the acetal mixture produced in Example 2 and 14.5 t of diethyl ether solvent for klO minutes. Niwata 9
added. In the middle of the exothermic reaction, ether was added again to remove the triethylamine hydrochloride from the thick slurry obtained from the reaction.

A clear orange product remained. The ether solvent was removed in vacuo to yield 4.72 of the crude product, which is liquid at ambient conditions. 2260tx- specific for nitrile and ester functional groups
Absorption bands were observed at 1740 cm-' and 1740 cm-'. They were also identified by nuclear magnetic resonance spectroscopy.

The product was a mixture of 2-(2-cyanoethyl)-4-acetoxymethyl-1,3-dioxolane and 2-(2-cyanoethyl)-5-acetoxy-1,3-dioxane.

Claims (1)

[Claims] 1. Formula: R" [In the above formula, R is hydrogen, phenyl, or branched or linear alkyl, and its cyano, hydroxy, alkoxy,
represents a monovalent group having 1 to 10 carbon atoms selected from the group consisting of acyloxy-5 or organosiloxy-substituted derivative groups; t-B represents branched or linear alkylene and -CCH2
2 to 1 carbon atoms selected from the group consisting of ), fOcH2CHCR, )-3, (where RxFi is hydrogen, methyl, or ethyl, and 愼 and 鴬 are 1 or an integer of 2 or more)
represents a divalent group having 0 gold; % R' is independently hydrogen and C9H2, alkoxy, aralkoxy, acyloxy or organosiloxy, and R is as defined above) Lv#: represents hydrogen or X, and Jl is zero or 1 represents, with the proviso that a
is zero, at least 1 R' is not hydrogen, and 8 is 1
2. R is hydrogen or methyl and B is a C2-6 branch. 3. The compound or mixture thereof according to claim 1, wherein X is hydroxy, acyloxy or organosiloxy, or a mixture thereof. 4. .2-(2-cyanoethyl)-4-hydroxymethyl-1,3-dioxolane, 2-(2-cyanoethyl)-
A compound according to claim 3 which is 5-hydroxy-1,3-dioxane or a mixture thereof. 5. The compound according to claim 3, which is 2-methyl-2-(3-cyanopropyl)-4-hydroxymethyl-1,3-dioquinrane. 6, 2-(1,1-dimethyl-3-cyanopropyl)
-4-hydroxymethyldioxolane, 2-(1,1-
4. A compound according to claim 3 which is dimethyl-3-cyanoprobyl)-5-hydroxydioxane or a mixture thereof. 7.2-(2-cyanoethyl)-4-)rimethersiloxymethyl-1,3-dioxolane, 2-(2-cyanoethyl)-5-trimethylsiloxy-1,3-dioxane or a mixture thereof A compound according to item 3 of the scope. 8.2-(2-cyanoethyl)-4-acetoxymethyl-1,3-dioquinrane, 2-(2-cyanoethyl)-
4. A compound according to claim 3, which is treated with 5-acetoxy-1,3-dioxane or a mixture thereof.