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3,437,693 United States Patent Office Patented Apr. 8, 1969 1. 2 3,437,693 SUMMARY OF THE INVENTION NITROHYDROXYETHERS John A. Frump, Terre Haute, Ind., assignor to Commer My invention relates to a new group of nitrogen com cial Solvents Corporation, New York, N.Y., a corpora pounds and a process for their preparation. More particu tion of Maryland larly, it relates to a catalytic process for oxyalkylating No Drawing. Continuation-in-part of application Ser. No. nitroalcohols and nitropolyols with epoxides and the novel 588,709, Oct. 24, 1966, which is a division of application nitro and amino-hydroxyethers obtained thereby. Ser. No. 302,470, Aug. 15, 1963, now Patent No. The novel nitrohydroxyethers, compounds A, of the 3,296,313, dated Jan. 3, 1967. This application Oct. 30, invention are those having the following general formula: 1967, Ser. No. 679,171 Int. C. C07c43/20, 77/02 A01n 9/24 10 R U.S. C. 260-61 1. Clain R-C-(CHR)-R,NO2 ABSTRACT OF THE DISCLOSURE wherein R4 is a member selected from the group consist 15 ing of methyl and hydrogen; wherein R1 is a member Nitrohydroxyethers of the formula selected from the group consisting of alkyl radicals, for R instance, of about 1 to 10 or 20 carbon atoms including lower alkyl radicals; lower hydroxyalkyl radicals for in R-(-(CHR) x-R2 stance, of up to 5 carbon atoms; and a radical having the No. 20 general formula: -(CH2)-R2, wherein R2 in the above wherein R4 is a member selected from the group consisting formula and radical is a member selected from the group of methyl and hydrogen; wherein R1 is a member selected consisting of the radicals from the group consisting of alkyl radicals, for instance, of about 1 to 10 or 20 carbon atoms, including lower (a) O-C H- H-OH alkyl radicals; lower hydroxyalkyl radicals, for instance, 25 R3 of up to 5 carbon atoms; and a radical having the formula and -(CH2)-R; wherein R2 in the above formula and (b) R radical is selected from the group consisting of IO-CH-CH)yOH 30 -o-CH-i-H-CH-O-OH--R,ÖH. ÖH. NO2 k wherein R3 is a member selected from the group consist and ing of hydrogen, phenyl, nitro-substituted phenyl, halo substituted phenyl, alkyl, hydroxy-substituted alkyl, halo R1 substituted alkyl, alkene, and phenyl-substituted alkyl -O-C-C-CH-C H-O-CH-)-R, radicals; y is an integer ranging from about 1 to 10 or 20, and x in the above formula and radical is an integer ÖH. ÖH. No. ranging from about 1 to 20. wherein R3 is a member selected from the group consist The novel nitro compounds of my invention can be ing of hydrogen, phenyl, nitro-substituted phenyl, halo prepared by contacting an epoxide with a nitroalcohol substituted phenyl, hydroxy-substituted alkyl, halo-sub 40 having the formula: stituted alkyl, alkene and phenyl-substituted alkyl radicals; y is an integer ranging from 1 to 10 or 20 and x in the above formula and radical is an integer ranging from R--(CHR) on about 1 to 20 which are useful in preparing the corre NO2 sponding amino compounds. Exemplary of such com wherein R4 has the above meaning and wherein R is a pounds is 2,11 - dimethyl-2,11-dinitro-4,9-dioxa-6,7-dihy member selected from the group consisting of alkyl radi droxydodecane. cals of 1 to 20 carbon atoms, for instance, including lower Aminohydroxyethers of the formula alkyl radicals; and lower hydroxy alkyl radicals, for in stance, having from about 1 to 5 carbon atoms; and x 50 is an integer ranging from about 1 to 20, in the presence R of catalytic amounts of boron trifluoride or p-xylenesul R-(-(CHR) x-R2 fonic acid. Examples of suitable nitroalcohols are NE 2-nitro-2-methyl-1-propanol, wherein R1, R2, R3, Ra, X and y have the values assigned 3-nitro-3-methyl-2-butanol, them above which are useful as corrosioon inhibitors, 55 tris(hydroxymethyl)-nitromethane, bactericides, pigment wetting and dispersing agents, emul 2-nitro-2-propyl-1-propanol, sifiers and intermediates in the preparation of non-ionic 2-nitro-2-methyl-1-octanol, surface active agents. Examplary of such amino-hydroxy 2-nitro-2-propyl-1-tridecanol, ethers is 2,11 - dimethyl - 6,7-dihydroxy-4,9-dioxa-2, 11 2-nitro-2-ethyl-1-nonadecanol, dodecanediamine. 60 12-nitro-12-methyl-1-tridecanol, 18-nitro-18-methyl-1-nonadecanol, 6-nitro-6-ethyl-1-heptanol, tris(hydroxyethyl) nitromethane, CROSS REFERENCE TO RELATED APPLICATIONS tris(hydroxybutyl) nitromethane, This application is a continuation-in-part of copending 65 application Ser. No. 588,709, filed Oct. 24, 1966 and now and the like. abandoned. Application Ser. No. 588,709 is a division of application Ser. No. 302,470, filed Aug. 15, 1963, and DETAILED DESCRIPTION now U.S. Patent No. 3,296,313. Application Ser. No. In the process for producing my new nitro compounds, 302,470 is a continuation-in-part of abandoned application 70 I generally employ temperatures ranging from about 0° C. to about 150° C. At temperatures above 150° C. de Ser. No. 8,234, filed Feb. 12, 1960. composition of the new compounds may occur. Temper 3,437,693 3 4. atures below 0° C., even though allowing formation of tain these aminohydroxyethers by oxyalkylation of the my new compounds, would not be economically prac corresponding amino alcohols proved unsuccessful since tical due to the requirement for expensive cooling equip the oxylating agents were found to preferentially add ment. While a broad temperature range of from about onto the amino group rather than the hydroxyl group. 25 C. to about 150° C., for instance, is suitable for my This preferential addition is expected since the amino process, I prefer to use temperatures ranging from about group is more reactive than the hydroxyl group and it 60° C. or 90° C. to about 130° C. When temperatures was thus surprising to find that the novel amine com below the melting points of the nitroalcohols used in my pounds of the present invention could be produced by invention are utilized, I prefer to use a solvent for the oxyalkylating the novel nitro compounds to the corre nitroalcohol which solvent is inert to the reactants and sponding novel amine compounds of the present inven the reaction product. Examples of solvents which are 0 tion. Because the amino compounds of the present in useful include isopropyl ether, chloroform, dioxane, and vention are more stable and can be titrated, the structures the like. of the nitro compounds are more easily determined in Satisfactory results can be obtained in my process for terms of the structures of the corresponding amino com producing the novel compounds of my invention by using 15 pounds. small or catalytic amounts of boron-trifluoride or p In another aspect, the method of my invention affords xylenesulfonic acid catalyst in the reaction mixture. It the production of a novel group of aminohydroxyethers was surprising to discover these catalysts since other having the structural formula that corresponds to that of acidic catalysts were found to be unsatisfactory. Catalytic the novel amino compounds given above for compounds amounts of boron trifluoride or p-xylenesulfonic acid 20 B with the proviso that only one of the R's in the formula ranging from about 0.05 to about 0.5% or 5% based on is an alkyl group and R2 is the radical the weight of the nitroalcohol can generally be utilized but boron trifluoride is preferred. However, if desired, to-CH-H-loitR more or less than this amount can be used. In utilizing the boron trifluoride catalyst in my process, I prefer to 25 wherein R3 and y have the same values assigned above. form a complex with a compound inert to the reactants In other words, the novel subgroup of aminohydroxy and the reaction products, for example, an ether. Rep ethers of the invention can be basically classified into resentative ethers which I have found to be useful in form three groups: ing complexes with boron trifluoride include isopropyl (I) R ether, dimethyl ether, diethyl ether, dibutyl ether, and 30 the like. I prefer a complex of boron trifluoride-diethyl R.--(CHR)-R, ether containing about 45 to about 50% by weight of NE boron trifluoride based on the weight of the complex. wherein R1 in each case is an alkyl group of up to 20 car Although free boron trifluoride is a suitable catalyst in bon atoms and R, R2 and x have the values assigned my process, its complexes with the ethers aforenamed are above, much easier to handle, use and store under ordinary in (II) The same formula wherein only one of the R's dustrial conditions, thus making them preferable to free is an alkyl group and the other is lower hydroxyalkyl, and borontrifluoride. R2 is the radical The molecular proportions used in producing the new R compounds of my invention can vary considerably de 40 pending on the nitroalcohol and epoxide used and/or on the final product desired. Ordinarily, mole ratios of nitro -o-CH.-E.-H-CH-O-CH--R,OH OH NH2 alcohol to epoxide of not less than 1:1 and not more wherein R1 has the value assigned above; and than about 1:10 or 1:20 are useful in my process. (III) The same formula as above wherein one R1 is The epoxides from which I prepare my compounds alkyl, the other is hydroxyalkyl and R2 is the radical must contain at least one O 3 –c4 Sc where R3 and y have the same values assigned above.
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    THÈSE PRÉSENTÉE A L’UNIVERSITÉ DE BORDEAUX ÉCOLE DOCTORALE DES SCIENCES CHIMIQUES POUR L’OBTENTION DU GRADE DE DOCTEUR SPÉCIALITÉ : CHIMIE ORGANIQUE Par Obinna Uchechukwu OSUJI TOWARD THE TOTAL SYNTHESIS OF BBIQ ALKALOIDS: THE TRILOBINE Directeurs de thèse : Frédéric CANTAGREL Eric FOUQUET Soutenue le: 19 Novembre 2020 Jury: M. Yannick LANDAIS Professeur, Université de Bordeaux Président Mme. Camille OGER Maître de Conférences, Université de Montpellier Rapportrice M. Laurent ELKAIM Directeur de Recherche-ENSTA Rapporteur Mme. Paola ARIMONDO Directrice de Recherche-Institut Pasteur Examinatrice M. Frédéric CANTAGREL Ingénieur de recherche, CNRS Directeur de thèse M. Eric FOUQUET Professeur, Université de Bordeaux Directeur de thèse 1 DEDICATION This research work is dedicated to Chimamanda, Munachisom, and Chibuikem with special thanks and love to Chizoba Obinna Osuji, wife, friend, and companion. And to the members of my family; for their prayers, unconditional love, and moral support, which has allowed me to complete this great landmark in my career. 2 ACKNOWLEDGEMENT This work is the result of a lifetime of learning and development from many mentors, teachers, supporters, advisors, counsellors, friends and family; who invested their time, energy and interest in my life. For this, I am eternally grateful. No achievement in life is without the help of many individuals known and unknown, who contributed to my life and I owe any measure of success to the array of inputs from them all. Here are just a few who made this work possible. To my dear parents, Sir Chukwuemeka and Lady Adaugo Osuji; and my ever interested, encouraging and enthusiastic siblings. You were always keen on my well-being, and the progress of my study in France.