Патент USA US2409087код для вставки
2,49%,‘085 Patented Oct. 8, 1946 UNITE STATES :PATENT OFFICE 2,409,086 REAUEIQN PRODUCTS OF NITRILES AND ALDEHYDES Joseph Frederic Walker, Lewiston, N. Y., assignor to E. 1. du Pont de Nemours & Company, Wil mington, DeL, a corporation of Delaware No Drawing. Application May 1,1943, ‘ Serial No. 485,361 _ 1- '1 Claim. (Cl. 260-464) . This invention relates to reactions between or ganic carbonyl compounds and ethylenic unsatu rated compounds, and to the novel chemical products resulting therefrom. More particularly, gives products di?erent in character from those it is directed to certain novel reactions between resulting when higher aldehydes are reacted. aliphatic aldehydes, including aldehydes contain _, I Examples of aldehydes which may be utilized. in my process are acetaldehyde,propionaldehyde, ing alkyl, aryl, cycloaliphatic, and aralkyl sub stituents, and acrylonitrile, and to the new and butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, heptaldehyde, phenylacetalde4 useful chemical compounds resulting from these 10 reactions. '2 " drogen. atom attached- to a carbon atom posi tioned alpha to the aldehyde group, is not one of the reactants which I employ in the reaction with,“ acrylonitrile, as I have found that formaldehyde ’ hyde, hydrocinnamaldehyde, etc. It is an object of this invention to produce by reaction of acrylom‘trile and aldehydes new and valuable chemical compounds containing one or more B-cyanoethyl groups attached to that car bon atom which is positioned adjacent to the al In the reaction it is possible to introduce one ?-cyanoethyl group in place of a hydrogen atom attached to the carbon atom which is positioned 15 adjacent the aldehyde group or two or three 13 cyanoethyl groups may beintroduced where this carbon atom contains two .or three replaceable hydrogen atoms. Thus, with acetaldehyde, it is dehyde group in the particular aldehyde reacted with acrylonitrile. It is, moreover, another ob ject of my invention to provide a method for car possible to produce B-cyanoethyl acetaldehyde rying out such reactions in the presence of alka CNCl-IzCI-IzCHzCl-IO by introducing one B-cyano line condensing agents. Another object of my 20 ethyl group in place of a reactive hydrogen atom invention is to provide a method for preparing positioned alpha to the aldehyde group. Similar new chemical compounds, the aldehydonitriles having the generic formula ly, it is possible ‘to introduce two B-cyan'oethyl groups to form y-formyl pimelonitrile 25 or tri-1,'1,l,-(pi-cyanoethyl)acetaldehyde by the where R1 is hydrogen or methyl and R2 is hydro gen, methyl, or p-cyanoethyl. These and still further objects of my invention will be apparent replacement of three reactive hydrogen atoms by c-cyanoethyl groups. Of course where there are less than three reactive hydrogen atoms on the carbon atom adjacent the aldehyde group, as in from the ensuing disclosure of certain preferred embodiments thereof. The aldehydes which, in accordance with my invention, are reacted with acrylonitrile (vinyl cyanide) are those having at least one active hy drogen atom' attached to the carbon atom which is positioned alpha to the aldehyde group. They may be characterized generically as compounds of the chemical constitution: 40 Y \ NC CHnCHz-(iJH-CHzCHaCN HCO propionaldehyde or isobutyraldehyde the number of ls-cyanoethyl groups replacing hydrogen on this carbon atom cannot exceed the number of reactive hydrogen atoms attached thereto. In carrying out the reaction the acrylonitrile and aldehyde are brought together in the pres ence of a substance which is alkaline in reaction. Any of the usual alkaline condensing agents have been found effective in promoting the reaction. These alkaline condensing agents are generally more alkaline than sodium carbonate, although Z with less alkaline compounds, such for example wherein Y and Z represent hydrogen, alkyl, aryl, 45 as the alkyl amines, the reaction will proceed but cycloaliphatic and aralkyl radicals, the radicals generally at a slower rate. Among alkaline con CH-CHO Y and Z being the same or different organic groups. When acrylonitrile is reacted with an aldehyde of the above-identi?ed formula in which Y and Z are both alkyl groups, the resultant product will be a cyano-ethyl di-alkyl aldehyde in which the two alkyl groups are joined to the carbon atom alpha to the aldehyde group. It is obvious from the foregoing de?nition that formaldehyde, which does not have a reactive hy densing agents which I have found particularly useful in the process may be mentioned the ‘alkali _metal and alkaline earth metal oxides, hydrox ides, carbonates, hydrides, cyanides and alcohol ates, as well as the alkali metals themselves, as for example, metallic sodium. The'alkali metal hydroxides and cyanides, as sodium hydroxide and sodium cyanide, have been found particu 55 larly effective. 2,409,086 4 Generally the catalyst or condensing agent stirrer, a re?ux condenser and a thermometer. Five cubic centimeters of a saturated solution of sodium hydroxide was added as alkaline condens ing agent and the reaction mixture was agitated and heated at re?ux temperature for two hours. should be present in amounts sufiicient to render the reaction mixture alkaline in reaction. Amounts ranging from 0.5% to 10% by weight, based on the weight of the reaction mixture, are suitable. With relatively stronger alkaline con densing agents, such as metallic sodium and the alkali metal hydroxides and cyanides, amounts A reddish-orange colored solution resulted, and the re?ux temperature rose gradually during the course of the reaction from 65° C. to about 80° C. not exceeding 3% will ordinarily be found to give Precautions were observed during the reaction to satisfactory results. 10 maintain the temperature at or below 80° C. The Since the reaction is exothermic in character, resulting mixture, after cooling and neutraliz after initially bringing the reaction mixture to ing with hydrochloric acid, was distilled at a the reaction temperature, one within the range pressure slightly below atmospheric in order to 0 to 100° 0., further heating is unnecessary and remove unreacted material. cooling may be necessary to dissipate any exces 16 The residue was distilled at a pressure of 3 sive amount of heat developed. The reaction may mm. A product boiling at 125° C. to 135° C. at be carried out without employment of diluting 3 millimeters of mercury pressure was obtained, agents, but if diluents are added I have found along with a fraction boiling at 100° C. to 115° inert liquids such as hexane, benzene, ether, and C. at 3 millimeters of mercury pressure. The petroleum ether most satisfactory. 20 latter was isobutyraldol. The higher boiling The particular sequence of adding the reagents product was identi?ed as a,a-dimethyl-~/-cyano is unimportant, as all that is necessary in order butyraldehyde. By operation in this manner that the reaction may proceed is to bring the re yields of ¢,a-dimethyl-'y-cyanobutyraldehyde cor agents together in intimate admixture in the responding to 35 to ‘10% of theory may be realized. presence of the alkaline condensing agent. In 25 Example 3 practice it is generally preferred ?rst to mix the aldehyde and acrylonitrile, and then introduce Five cc. of a saturated solution of sodium hy the alkaline condensing agent, at the same time droxide was added cautiously to 212 grams (4 applying initial heating, if necessary, in order to mols) of acrylonitrile heated under re?ux. To bring the contents of the reaction vessel to a 30 the resulting mixture there was then added, in temperature at which the reaction will proceed small increments, 58 grams (1 mol) of propion rapidly and smoothly. aldehyde, after which the mixture was cooled The products resulting by reaction of acryloni and treated for recovery of product as in Ex trile with aldehydes, the new aldehydonitriles, are ample 1. valuable as intermediates in the preparation of 35 Two products were obtained. The ?rst chem a large number of organic compounds and for ical compound boiled at 92° C. to 94° C. at 3 mil other purposes, such as in the manufacture of limeters of mercury pressure, and had molecular plastic products. weight and nitrogen content corresponding to The following examples illustrate this inven tion: , Example 1 a - methyl - 'y - cyanobutyraldehyde. The second 40 chemical compound boiled at 135.5° ‘C. to 137° C. at 3 millimeters pressure, and was identi?ed as 'y-methyl-y-formyl-pimelonitrile. The yields ' In a one-liter ?ask ?tted with a stirrer, a re flux condenser, a thermometer and a delivery of the lower-boiling and higher-boiling products tube extending to a point adjacent the bottom of were 4.9% and 25.1 %, respectively. the ?ask, there was placed 212 grams (4 mols) 45 of acrylonitrile. While stirring and heating un ' ' ‘Example '4 Acrylonitrile (4 mols) and acetaldehyde (2 der re?ux were continued, 3 cc. of a 50% solution mols) were reacted as described in Example‘l of sodium hydroxide was added to the acryloni utilizing sodium cyanide as alkaline condensing trile, after which 88 grams (2 mols) of acetal dehyde was vaporized and the vapors passed 50 agent in place of sodium hydroxide.v The com bined yield of 'y-cyanobutyraldehyde and 7-for into the acrylonitrile. The rate of addition of myl-pimelonitrile was 38% of the theoretical the acetaldehyde was controlled so as to pre based on the amount of acetaldehyde reacted. vent heat surges. The addition required about The new chemical compounds produced by re 2 to 3 hours, after which stirring was continued for an additional period of one hour. 55 acting aldehydes and acrylonitrile, in accordance with the process described, are those character ized generically by the formula: with dilute hydrochloric acid, and unreacted ma terials were distilled off. The resulting residue was subjected to vacuum distillation whereby products boiling at 86° C. to 95° C., and 145° C. 60 The resulting mixture was cooled, neutralized to 149° C., at a pressure of 3 millimeters of mer cury were obtained. The lower boiling material, identi?ed as y-cyanobutyraldehyde, had a molec said compounds being aldehydonitriles. In this generic formula R1 represents hydrogen or a ular weight and nitrogen content corresponding methyl group; and R2 represents hydrogen, meth to those values for that compound. The higher 65 yl, or the p-cyanoethyl radical (CNCH2CH2—~). boiling material was identi?ed as y-formyl Various changes may be made in the process pimelo-nitrile. The combined yield of the two for reacting acrylonitrile with aldehydes as here ‘products was about 40 to 50% of theoretical. in described which would come within the sco or‘ my invention. ' Example 2 70 I claim: A mixture of 72 grams (1 mol) of isobutyraL As a new chemical compound 'y-formyl pimelo dehyde and 159 grams (3 mols) of acrylonitrile nitrile. was placed in a reaction ?ask provided with a JOSEPH FREDERIC WALKER.