Патент USA US2406504код для вставки
Patented Aug. 27,‘ 1946 ‘ 2,406,504 I -UNITED-PST'ATES" PATENT OFFICE J ‘ NITRO KETALS m ‘teams Fort’ PREPARATION 'rHEaEoE' v _ Glen II. ‘Morey, Terre Haute, Ind}, assignor to Commercial Solvents Corporation, Terre Ilaute,_Ind., a corporation of Maryland; } , No Drawing. Application ‘at ‘29, 19.44,? p "1 Serial No. 547,283 g , '" 8 Claims. (01. 260-338) ‘ l The present invention’ relates to a‘series of new‘ ketals and to a process for-,theirlpreparation. More particularly it pertains to ketals haVingJdi effected between any alkyl levulinate ‘and’ any 2- ‘ nitro-‘l_,.37propanediol. , The acid‘ catalyst utilized in producing the new versiiled'~v functional I groups. '1 ‘Speci?cally, such I ketals of my invention may be selected froma rel compounds may be graphically represented by'the following formula: v‘ Q j'FT ‘ ~"atively wide range of compounds. In fact, it may generally be saidthat‘ any acidv previously known to be capable of promoting esteri?cation will be satisfactory for my purpose. Speci?c examples of ~ °1i7°<i?i*‘’i*i*°i' , i 0 H2O o / “such acids are: p-toluene-sulfonic' acid, sulfuric ~ acid, hydrochloric acid, and the like. The alkyl levulinates and 2-nitro-1,3-propane 6H: I R\N 02 wherein the substituent R may be either hydrogen‘ diols employed in carrying'out the process of the present invention likewise maybe selected from a Y wide variety of compounds.- or alkyl, and R1 represents an alkyl group. Com pounds of the above type are prepared by reacting a suitable 2-nitro-1,3-propanediol with an alkyl levulinatepin the presencefof' a small" quantity of acid catalyst. The process is preferably? eifec'ted " 20_ by heating the reaction mixture in ltheiiprés‘en‘cei of an'inert water-'immiscibleli'quid‘such asbené zene, toluene or a similar substanceyiniorder 'to ‘ remove- the water produced substantially ' a's“‘it‘ is? formed. The reaction ' ‘mixture is preferably" heated at its re?ux temperature until?approxi mately the theoretical quantity of water has-been Typical examples of , alkyl levulinates operative in my process are methyl levulinate, butyl levulinate, hexyl'levulin ate, decyl levulinate, and the like.‘v Examples of suitable ‘2~nitro-‘1,3-propanedi0ls are 2-nitro-1,3 propanediol, 2-nitro-2-methy1-1,3-propanediol;2 nitric-2"-ethyI-L3-propanédiol, ‘,2 - nitro-2-propyl 1,3-propanediol, ‘2-nitroe2-butyl-1,3-propanedioh; and the like. . My invention may be furtherillustrated by the , following speci?c examples: Example, To a mixture consisting of 149 g. of '2-ethyl-2 removed. _ Thereafter, distillation is 'dis'continued;v and the mixture washed with water to-remove the nitro-1,3~propanediol, 200 g. of butyl levulinate catalyst. Separation of the inert water-immis-‘ toluene sulfonic acid. This mixture was then heated to re?ux temperature and the Water pro cible liquid and water, as well as other‘impurities is readily accomplished by distillation. The inert liquid and Water are removed at atmospheric pressure, while the higher boiling impurities, such and 300 .cc. of benzene, was added 1 g. of para duced during the ketalizationremoved with ben zene, the latter being continuously returned to the distillation ?ask. After about twenty-four as, unreacted alkyl levulinate or 2-nitro-1,3-pro— 35 hours, 16.5 cc. of water was removed, heating was ‘ panediol are separated from the ketal thus pro then discontinued, and the mixture washed with duced by distillation under reduced pressure. cold water. The major portion of the benzene Further purification of the desired product which was then distilled off at atmospheric pressure is obtained as a residue may be readily effected by 40 while the last portions thereof were removed at distillation under relatively high vacuum. 90° C. (30 mm.). The crude butyl-2-methyl-5 One of the highly surprising features of the ethyl-5-nitro-2-m-dioxanepropionate was then process of the present invention is the fact that distilled in vacuo. A fraction was collected be said process has been found to be operative only low 125° C. (5 mm.) and consisted chie?y of unre-' with 2-nitro-1,3-propanediols. Attempts to carry out the same type of reaction with the ordinary 45 acted butyl levulinate. The pure ketal boiled at 190° C. (3 mm.) and amounted to 219 g. corre glycols such as ethylene glycol or with the trihy sponding to a yield of 72% of theory. dric nitro alcohols, such as, tris(hydroxymethyl) nitromethane have been completely without suc Analysis: Calculated for C12H25NO6-gN, 4.62. cess. With the ordinary glycols, comp1ex mix— . Found: N, 5.15. tures of products are obtained, which cannot be 50 Example II separated, whereas, with compounds such as tris (hydroxymethyl) nitromethane, no reaction what In accordance with the procedure described in ever was observed to occur. In the case of the 2' nitro-1,3-propanedio1s, however, the reaction in Example I, ethyl 2-methyl-5-ethyl-5-nitro-2-m dioxane-propionate was prepared from 2-nitro volved appears to be quite general and is readily 55 2-ethyl-l,3-propanediol and ethyl levulinate in 4 3 V I prise mixing a 2-n'itro-1,3-pr0panedio1 with an’ the presence of approximately 1 g. of sulfuric: acid. The product thus obtained was a crystal-v line compound, melting at 83° C; and was ob tained in a yield corresponding to 60% of theory. alkyl levulinate in the presence of an esteri?ca tion catalyst and an inert water-immiscible liquid, heating the resultant mixtureto its re ?ux temperature, removing'the water in a vapor ous state with? said water-immiscibleliquiaand. _ Analysis: Calculated for C12H21NOs——N, 5.09. Found: N, 5.66. Molecular weight: found 269;‘ recovering the aforesaid’ substituted" 5-nitro-1,3- 7 theory, 275. . It is to be speci?cally understood that I in’ dioxane. 5. In a process ‘for the preparation of substi the present invention to _ ‘1' no Way desire to limit the compounds disclosed in the speci?c. examples ‘.10. -tuted. 5,-nitro-1,3-dioxanes of the formula: given above. On the contrary, as previously. in-. dicated, the process involved is generally appli-I ' cable to any alkyl levulinate and any 2-nitro+1,3‘- _ e ; a . ' i- ? propanediol. The new ketals of the present inventionhavef 15.. meg: on, e 0 been found to be useful ‘as placticizers for various . > ?lm formingrmaterials, particularly‘ thosecona ,; - sisting essentially of vinyl chloride polymers. .7 £\VNOn ' in'which the substituent B. represents a member ‘ Other uses of these compounds will be readily 20 selected from the ‘group consistingof hydrogen apparent to those skilled in the art. havingbeen described; what. and’ alkyl; and R1 is alkyl, the steps whichcom ‘ My invention now prise mixing} an alkylhlevulinate with a 2énitrow V I claim is: Y 1. Substituted 5.-nitro'-l,3-dioxanes l;3'-propanediol;in the presence of an'esteri?ca'i. the i following vgeneral formula; ‘ tion catalysir heating .the resultant mixture and ~ recovering‘ a compound of? the aforesaid g-formula. 125.; 6. In "a process for‘ the preparation of‘; sub-,- _ stituted 5-nitro-1,3,=dioxanes of the formula: V ' 30 wherein the- substituent B. represents, a. member ' selected fromthe group-consist‘mg: of; hydrogen and alkyl and R1 is alkyl, ' ‘ a 2. Butyl 2 - methyl #- 5 - ethyl - 5 - intro-2 ~ m ’ dioxane-propionate'. 5-ethyl-5-nitro-2-msdioxane - 'pro‘pionate. - \ I V _. V >4'.;In a’ process forthe preparation'ofgsube stitutedV-S-nitro--l,3+dioxanes having the‘ formula: - in which the substituentLR represents a member selected from'the group consisting of hydrogen is alkyl, the: steps-which com prise - mixing a Z-nitro-l?-p-propanediol with, - an ; reilkyllevulinateinthe presence of an esteri?ca» ‘heating the resultant ; _ _ n 7 tion catalyst-iandr‘benzene, mixture to its re?ux temperature,v removingrthe water inayaporous state with said benzene and 45 recovering'the, aforesaid substituted;5—nitrog1,3->I ‘ dioxane.‘ ,1 ‘5;’ - v V, . '1‘.>Theprocessof claim 6 in which the alkyl levulinate is ‘butyl levulinate and the -2-nitro-1=,3-v propanediol is 2-nitro-2-ethyl-1,3-propanediol. '8; The process of claim 6 in which the alkyl in which the substituent R represents a member selected from the class consisting of hydrogen‘ and halkyl. and B1 is alkyl, the steps which com: 50 levulinate is ethyl levulinate and the 2-nitro-l,3-é propanediol is 2-nitro-2-ethyl-1,3-propanediol. . ' ' - ' GLEN I-I. MOREY.