US2852512A - Adducts of heterocyclic amides - Google Patents

Adducts of heterocyclic amides Download PDF

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US2852512A
US2852512A US626311A US62631156A US2852512A US 2852512 A US2852512 A US 2852512A US 626311 A US626311 A US 626311A US 62631156 A US62631156 A US 62631156A US 2852512 A US2852512 A US 2852512A
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oxazin
methyl
oxazolidinone
methylene
thione
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US626311A
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Newman M Bortnick
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Rohm and Haas Co
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Rohm and Haas Co
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    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
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    • C07D239/08—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms directly attached in position 2
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    • C07D241/08—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
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    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
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    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/18—Oxygen atoms
    • C07D263/20—Oxygen atoms attached in position 2
    • C07D263/22—Oxygen atoms attached in position 2 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/02—1,2-Oxazines; Hydrogenated 1,2-oxazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
    • C07D265/08—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
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    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
    • C07D265/08—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D265/10—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with oxygen atoms directly attached to ring carbon atoms
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    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
    • C07D265/32—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings with oxygen atoms directly attached to ring carbon atoms
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C10M2215/224—Imidazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/30—Heterocyclic compounds
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds

Definitions

  • This invention concerns adducts of heterocyclic amides and specific nip-unsaturated compounds. It further deals with a method of preparation for these adducts.
  • the heterocyclic amides employed in this invention may be represented by the formula o H Y in which L is a threeto four-membered divalent chain containing two to three carbon atoms and one oxygen atom, and Y is a chalcogen having an atomic weight of sixteen to thirty-two, i. e., oxygen or sulfur.
  • the carbon atoms in the L chain may have their remaining valences satisfied by hydrogen atoms, by alkyl groups whose total carbon atom content is no greater than eighteen, or by combination of hydrogen and alkyl groups.
  • L contains two carbon atoms there are four valences to be satisfied by hydrogen atoms, alkyl groups, or combinations thereof.
  • L contains three carbon atoms there are six valences to be satisfied byhydrogen atoms, alkyl groups, or combinations thereof and these valences may be satisfied in a way analogous to the manner described above when L contained two carbon atoms. It is also possible for the above-mentioned alkyl substituents to be joined together to form carbocyclic rings in conjunction with the L chain.
  • the oxygen atom in the L chain be vicinal to the carbonyl group in the heterocyclic amide.
  • the alkyl substituents on the carbon atoms of the L chain may have any possible spatial configuration such as normal, iso-, tertiary, and the like. Typically, these alkyl substituents may also be straight chained or cyclic.
  • Typical of the alkyl substituents that may be used to satisfy the remaining valences of the carbon atoms in the L chain include methyl, ethyl, propyl, butyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, and octadecyl groups.
  • heterocyclic amidesthat may be employed as reactants in the present invention include 2- oxazolidinone, 4-oxazolidinone, 3-isooxazolidinone, tetrahydro 1,3 oxazin 2-one, 1,4oxazin-3-one, 1,3-oxazin- 4-one, 1,2-oxazin-3-one, S-methyl-Z-oxazolidinone, 4,5- dimethyl-Z-oxazolidinone, 5-butyl-2-oxazolidinone, 4-propyl-S-octyl-2-oxazolidinone, .4-cyclohexyl-Z-oxazolidinone, 4 ethyl 5 .dodecyl 2 oxazolidinone, 4,4,5,5 tetramethyl 2 oxazolidinone, 4 octadecyl 2 oxazolidinone, 2-methyl-4-oxazolidinone, 2,5-d
  • the a,fl-unsaturated compounds employed in this invention correspond to the torrnula in which Q is a hydrogen atom, an alkyl group of one to eight carbon atoms, or the group to be more fully described hereinafter.
  • T may stand for a cyano group, the group CONZ in which Z may stand for a hydrogen atom or an alkyl group of one to four carbon atoms, or the group -COOR.
  • R represents a monovalent esterifying group of preferably one' to fourteen carbon atoms and, preferably, alkyl groups of one to fourteen carbon atoms, alkoxyalkyl groups of two to fourteen carbon atoms, aralkyl and alkaralkyl groups of seven to fourteen carbon atoms, and cycloalkyl and alkyl'cycloalkyl groups of three to fourteen carbon atoms.
  • the alkyl groups may be straight or branched chains in any of the known spatial configurations.
  • the alkyl groups positioned on cyclic structures may occupy any possible ring location.
  • Typical of the representations of Q include a hydrogen atom, the groups methyl, ethyl, propyl, butyl, hexyl, and octyl, and the groups CH CH CH(CH )T.
  • Typical of the groups that may be employed as T include cyano, carbamoyl, methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, butylcarbamoyl, dimethylcarbamoyl, diethylcarbarnoyl, dibutylcarbamoyl, methylethylcarbamoyl, ethylbutylcarbamoyl, propylbutylcarbamoyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, octoxycarbonyl, dodecoxycarbonyl, tetradecoxycarbonyl, bonyl, methoxyethoxycarbonyl, methoxypropoxycarbonyl, methoxybutoxycarbonyl, methoxyoctoxycarbonyl, methoxydecoxycarbonyl, ethoxymethoxycarbonyl,
  • butoxydecoxycarbonyl pentoxymethoxycarbonyl, pentoxybutoxycarbonyl, pentoxypentoxycarbonyl, pentoxyhexoxycarbonyl, pentoxyoctoxycarbonyl, hexoxymethoxycarbonyl, hexoxypropoxycarbonyl, hexoxyhexoxycarbonyl, hexoxyoctoxycarbonyl, heptoxymethoxycarbonyl, heptoxybutoxycarbonyl, heptoxyheptoxycarbonyl, octoxymethoxycarbonyl, octoxyethoxycarbonyl, octoxybutoxycarbonyl, octoxyhexoxycarbonyl, benzoxycarbonyl, phenylethoxycarbonyl, phenylbutoxycarbonyl, ethylbenzoxycarbonyl, phenylbutoxycarbonyl, phenylhexoxycarbonyl, phenyloctoxycarbonyl, butylbenz
  • Illustrative of the a,fl-unsaturated compounds that may be used as reactants in this invention include acrylonitrile. methacrylonitrile, u-butylacrylonitrile, u-octylacrylonitrile, acrylamide, methacrylamide, u-ethylacrylamide, m-propylacrylamide, a-octylacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylmethacrylamide, N-ethyl-N-propyltnethacrylamide, N-methyl-aethylacrylamide, N-methyl-N-butyl-a-propylacrylamide, N,N-di-(2-ethylhexyl) acrylamide, N,N-dimethyl-uoctylacrylamide, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecy
  • the products of this invention are made by bringing together at a reacting temperature in the. presence of a strong alkaline catalyst 21 compound having the formula Q. with one having the formula CHFG-T ataxia solvent such as methanol, i ethanol, butanol, benzene, toluene, xylene, dioxane, diethyl'ether, dimethyl ether of ethylene glycol, and the like.
  • a strong alkaline catalyst 21 compound having the formula Q. with one having the formula CHFG-T ataxia solvent such as methanol, i ethanol, butanol, benzene, toluene, xylene, dioxane, diethyl'ether, dimethyl ether of ethylene glycol, and the like.
  • a solvent such as methanol, i ethanol, butanol, benzene, toluene, xylene, dioxane, diethyl'ether, dimethyl ether of ethylene glyco
  • the present reaction is exothermic in nature and it is frequently advantageous to conduct the reaction by first adding all of the predetermined equivalent amount.
  • the present reaction is consistently conducted in an orderly manner.
  • the time of reaction is not critical. Generally, times of about one-half hour to twenty-four hours are used, as conditions indicate. It is usually advantageous to conduct the present method for about an hour or two after the heat of reaction is finally dissipated. This is to maximize yields. Otherwise, the-reaction may be concluded as one skilled in the art finds desirable.
  • a strong alkaline catalyst is used to effect the present method.
  • alkali metals such as lithium, sodium, and potassium; alkali metal oxides such as lithium oxide, sodium oxide, and potassium oxide; alkali metal lower alkoxides such as lithium butoxide, sodium methoxide, and potassium ethoxide; alkali metal hydrides such as sodium hydride and potassium 'hydride; alkali metal amides such as sodium amide, lithium amide, and potassium amide; alkali metal lower alkyls and alkenyls such as methyl lithium, ethyl sodium, butyl potassium, allyl sodium, and 'butenyl potassium;
  • phenylalkyl alkali metals such as benzyl sodium, phenylisopropyl potassium, and alkali metal aromatics such as phenyl sodium, phenyl lithium and phenyl potassium, phenyl butyl sodium
  • Alfin catalysts which are commercial mixtures of alkali metal alkenyls and alkali metal alkenoxides, such as allyl sodium with' sodium allyloxide and butenyl potassium with sodium butenyloxide
  • quaternary ammonium bases such as trimethylbenzylammonium hydroxide and dimethyldibenzylammonium hydroxide and the corresponding alkoxides such as trimethylbenzylammonium butoxide, choline methoxide, and the like.
  • reaction system may be added to the reaction system enough anhydrous mineral acid such as sulfuric, phosphoric, or the like, to neutralize the catalyst.
  • the salt formed may be removed such as by filtration. Otherwise, the reaction system may be washed with water and the aqueous layer separated or decanted when the product is a solid. Any solvent employed may 'be stripped off, preferably under reduced pressure. Unused reactants when present may be Washed out with water or stripped off under reduced. pressure. If the product is a liquid it may be distilled,if desired.
  • Solid prod ucts may be recrystallized ina conventional mannerfrom a suitable solvent such as hexane, gheptane, benzene, toluene, ethylene dichloride, chloroform, or the like.
  • Transesterification may be conducted preferably in the presence of a strongly acidic esterifying catalyst including sulfuric acid, a lower alkanesulfonic acid, such as butanesulfonic acid, and an arylsulfonic acid, such as p-toluenesu-lfonic acid. It is, also, possible to employ a strongly acidic ion-exchange resin, such as a sulfonated polystyrene or sulfonated phenolformaldehyde resin.
  • a strongly acidic esterifying catalyst including sulfuric acid, a lower alkanesulfonic acid, such as butanesulfonic acid, and an arylsulfonic acid, such as p-toluenesu-lfonic acid.
  • a strongly acidic ion-exchange resin such as a sulfonated polystyrene or sulfonated phenolformaldehyde resin.
  • Transesterification is preferably conducted at the reflux temperature of the reaction mixture, which is usually in the range of about to 275 0, preferably in the range of about to 225 C.
  • the pressure is adjusted,
  • an inert volatile organic solvent such as toluene, xylene, or the like, may be used 'to help regulate the reflux temperature.
  • an inert volatile organic solvent such as toluene, xylene, or the like.
  • the product is isolated such as by neutralizing the catalyst, filtering, and distilling, preferably under reduced pressure.
  • the products of this invention have a wide variety of valuable utilities.
  • the lower molecular weight members are excellent solvents for polymers particularly those in which 'acrylonitrile or a vinyl ester is the major component.
  • the liquid members are useful as synthetic lubricants in which instances they consistently exhibit high viscosity indexes, low pour points, and low volatilities.
  • the present products are useful as plasticizers, particularly for polyvinyl chloride. For instance, a mixture of 28 parts of 3 (2-methoxycarbonylethyl)-2-oxazolidinone, 44 parts of polyvinyl chloride, 0.75 part of tribasic lead sulfate, and 0.4 part of stearic acid milled for seven minutes at 325 F.
  • the present products are effective fungicides when applied against Stemphylium mimeforme and especially Monilinia fructicola in concentrations up to 1.0% in an'inert carrier. These products are at the same time non-phytotoxic in concentrations approaching 1% as determined on tomato plants in a standard test.
  • Example 3 Into a reaction vessel there areadded 14.3 parts of 4,4,5,5-tetramethyl-Z-oxazolidinone and 0.25 part of sodium methoxide. Over a 10-minute period there is added 19.2 parts of butyl acrylate. The temperature of the reaction system rises from the exothermic heat of reaction. There is then introduced 0.50 additional part of sodium methoxide in two equal installments 20 minutes apart. The temperature of the reaction mixture is maintained at 105 to 115 C. for three hours. The catalyst is neutralized by the addition of phosphoric acid and the product is isolated by distillation. The product is identified as 3-(Z-butoxycarbonylethyl)-4,4,5,5-tetramethyl-Z-oxazolidinone.
  • Example 4 There are introduced into a reaction vessel five parts of 3-isooxazolidinone and 0.25 part of potassium ethoxide. The mixture is heated to 72 C. and ten parts of methyl methacrylate is added over a period of ten minutes causing the temperature to rise. After 30minutes there is then added 0.25 part of potassium ethoxide causing a further temperature rise. When the heat of reaction abates the mixture is heated at 130 to 136 C. for 40 minutes. The catalyst is neutralized by the addition of phosphoric acid and the product is isolated by distillation. The product corresponds to 2(2-methoxycarbonylpropyl -3 -isooxazolidinone.
  • reaction vessel 20.2 parts of tetrahydro-1,3-oxazin-2-one and two parts of potassium butoxide. There isadded 20 parts of diethyl-mmethylene-a,methyladipate over a period of 15 minutes. The reaction mixture is heated to 82 C. and 1.2 parts of potassium butoxide is added. There is then added dropwise 25 parts of diethyl a-methylene-a'-methyladipate and one part of potassium butoxide. The reaction mixture is heated at 98 to 120 C. for two and one-half hours. There are then added 300 parts of toluene and 100 parts of an aqueous 20% solution of sodium carbonate.
  • the reaction mixture is stirred rapidly and the organic layer is separated, Washed with 100 parts of aqueous 10% phosphoric acid, and then washed with 100 parts of water, The organic layer is stripped to 160 C. at 0.1 mm. absolute pressure leaving the product as the residue.
  • the product is identified as 3(2,5-diethoxycarbonylhexyl)-tetrahydro-l,3-oxazin-2-one.
  • Example 6 Into a reaction vessel there are added 47 parts of tetrahydro-1,3-oxazin-2-thione, 200 parts of toluene and three parts of potassium hydride. There is then added dropwise over a period of minutes 30 parts of acrylonitrile at such a rate that the temperature of the reaction mixture, maintained by the exothermic heat of reaction, is kept below C. The reaction mixture is then allowed to stand for one hour. The toluene layer is removed and anhydrous phosphoric acid is added to neutralize the catalyst. The toluene is removed by stripping at reduced pressure and the product is added by distillation at reduced pressure. The product corresponds to 3- (2-cyanoethyl) -tetrahydrol ,3-oxazin-2-thione.
  • Example 7 After two additional hours the catalyst is neutralized with sulfuric acid. The product is isolated by distillation at reduced pressure.
  • the product corresponds to 4(2- cyanoethyl)-tetrahydro-1,4-oxazin-3-thione.
  • Example 8 There are mixed in a reaction vessel 20 parts of 2-butyl-5,S-dimethyltetrahydro-1,3-oXazin-4-one and 20 parts of methyl methacrylate. There is added two parts of sodium methoxide in 0.5 part portions at 10-minute intervals. The reaction mixture is then heated to 112 to 118 C. for three hours. Phosphoric acid is added to neutralize the catalyst. The product'is isolated by distillation at reduced pressure. The compound corresponds to 2 butyl 3 (2 methoxycarbonylpropyl) 5,5 dimethyltetrahydro 1,3-oxazin-4-one.
  • Example 9 There are added to a reaction flask 2O par-ts of 6-penty1- Example 10 There are charged to a reaction vessel parts of 3-(2-methoxycarbonylethy1) -2-oxazolidinone and 52 parts of Z-ethylhexanol. The solution is heated at reflux until water no longer collects in a Dean-Stark separator attached to the vessel. There is added five parts of sulfuric acid and the water separator is replaced by a column and distilling head. The reaction mixture is held at to 150 C. Methanol is removed until the theoretical amount is collected. The reaction mixture is washed with two -part portions of aqueous 20% sodium carbonate and'lSO parts of water and then dried over anhydrous magnesium sulfate. Two parts of phosphoric acid is added and the mixture is distilled and the product collected at reduced pressure. The product is identified as 3 [2-(2-ethylhexoxy carbonylethyll -2-oxazolidinone.
  • T-OHOHa atom the available valencs of said two to three carbon atoms in said L chain being satisfied by members from the group consisting of a hydrogen atom and alkyl groups whose total carbon content is no greater than eighteen
  • Y is a chalcogen having an atomic weight of 16 to 32
  • Q is a member from the group consisting of a hydrogen atom, alkyl groups" or one to eightcarbon atoms
  • T is a member from the group consisting o f a cyanogroup
  • alkyl portion contains one to fourteen carbon. atoms, andlthe' alk portion contains one to eight carbon atoms.” 7
  • n is an integer of one to nine.
  • Nrno c oncml in which in is an integer of one to nine.
  • composition .of matter 3-(2-ethoxycarbonylethyl)-tetrahydro-1,3-oxazin-2-one.
  • L is a threeto four-membered divalent chain containing two to three carbon atoms and one oxygen atom, the available valences of said two to three carbon atoms in said L chain being satisfied by members from the group consisting of a hydrogen atom and alkyl groups whose total carbon content is no greater than eighteen
  • Y is a chalcogen having an atomic weight of 16 to 32
  • Q is a member from the group consisting of a hydrogen atom, alkyl' groups of one to eight, carbon atoms, and the group -CH CH CH(CH )T
  • T is a member from the group consisting of a cyano "group
  • the group -COOR in which R is a member from the group consisting of alkyl groups of one to fourteen carbon atoms
  • the alkyl portioncontains one to fourteen carbon atoms which comprises bringing together at areacting temperature in the range of about 0 to 200 C. in the presence of a strong alkaline catalyst, 2-oxazolidinone and a dialkyl nt-methylene-d'-methyladipate.
  • a method for the preparation of 4-(2-carbamoy1- ethyl)-2,6-diethyltetrahydro-1,4-oxazin-3-one which comprises bringing together at a reacting temperature in the 14 range of about 0 to 200 C. in the presence of a strong alkaline catalyst, 2,6-diethyltetrahydro-l,4-oxazin-3-one and acrylamide.
  • a method for the preparation of 3-(2-ethoxycarbonylethyl)tetrahydro-l,3-oxazin-2-one which comprises bringing together at a reacting temperature in the range of about 0 to 200 C. in the presence of a strong a1- kaline catalyst, tetrahydro- 1,3-oxazin-2-one and ethyl acrylate.
  • a method for the preparation of 3-(2,5-diethoxyc-arbonylhexyl)-tetrahydro-1,3-oxazin-2-one which comprises bringing together at a reacting temperature in the range of about 0 to 200 C. in the presence of a strong alkaline catalyst, tetrahydro-1,3-oxazin-2-one and diethyl a-methylene-a'-methy1adipate.
  • a method for the preparation of 3-(2-cyanoethy1)- tetrahydro-l,3-oxazin-2-thione which comprises bringing together at a reacting temperature in the range of about 0 to 200 C. in the presence of a strong alkaline cata- 20 lyst, tetrahydro-l,3-oxazin-2-thione and acrylonitr-ile.

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Description

United States Patent 2,852,512 ADDUCTS F HETEROCYCLIC AMIDES Newman M. Bortnick, Oreland, Pa., assignor to Robin & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application December 5, 1956 Serial No. 626,311
24 Claims. (Cl. 260-244) This invention concerns adducts of heterocyclic amides and specific nip-unsaturated compounds. It further deals with a method of preparation for these adducts.
The heterocyclic amides employed in this invention may be represented by the formula o H Y in which L is a threeto four-membered divalent chain containing two to three carbon atoms and one oxygen atom, and Y is a chalcogen having an atomic weight of sixteen to thirty-two, i. e., oxygen or sulfur. The carbon atoms in the L chain may have their remaining valences satisfied by hydrogen atoms, by alkyl groups whose total carbon atom content is no greater than eighteen, or by combination of hydrogen and alkyl groups. When L contains two carbon atoms there are four valences to be satisfied by hydrogen atoms, alkyl groups, or combinations thereof. 'For instance, there may be four hydrogen atoms, four alkyl groups, three hydrogen atoms and one alkyl group, two hydrogen atoms and two alkyl groups, or one hydrogen atom and three alkyl groups. When L contains three carbon atoms there are six valences to be satisfied byhydrogen atoms, alkyl groups, or combinations thereof and these valences may be satisfied in a way analogous to the manner described above when L contained two carbon atoms. It is also possible for the above-mentioned alkyl substituents to be joined together to form carbocyclic rings in conjunction with the L chain.
it is preferred that the oxygen atom in the L chain be vicinal to the carbonyl group in the heterocyclic amide. The alkyl substituents on the carbon atoms of the L chain may have any possible spatial configuration such as normal, iso-, tertiary, and the like. Typically, these alkyl substituents may also be straight chained or cyclic. Typical of the alkyl substituents that may be used to satisfy the remaining valences of the carbon atoms in the L chain include methyl, ethyl, propyl, butyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, and octadecyl groups.
Illustrative of the heterocyclic amidesthat may be employed as reactants in the present invention include 2- oxazolidinone, 4-oxazolidinone, 3-isooxazolidinone, tetrahydro 1,3 oxazin 2-one, 1,4oxazin-3-one, 1,3-oxazin- 4-one, 1,2-oxazin-3-one, S-methyl-Z-oxazolidinone, 4,5- dimethyl-Z-oxazolidinone, 5-butyl-2-oxazolidinone, 4-propyl-S-octyl-2-oxazolidinone, .4-cyclohexyl-Z-oxazolidinone, 4 ethyl 5 .dodecyl 2 oxazolidinone, 4,4,5,5 tetramethyl 2 oxazolidinone, 4 octadecyl 2 oxazolidinone, 2-methyl-4-oxazolidinone, 2,5-dipropyl-4-oxazolidinone, 2,2,5,5-tetramethyl-4-oxazolidinone, Z-methyl- -5 -.octy1-4 oxazolidinone, 2-cyclopentyl-4-oxazolidinone,
2-propyl-5-decyl-4-oxazolidinone, 2-decyl-5-octyl-4- oxazolidinone, 2,2-diethyl-5-hexyl-4-oxazolidinone 4-methyl-* 2 3-isooxazolidinone, 5-methyl-3-isooxazo1idinone, 4-ethy1- 5 octyl 3' isooxazolidinone, 4,4 diethyl 3 isooxazolidinone, 4,5-dipropyl 3 isooxazolidinone, 4-octy1- 5-decyl-3-isooxazolidinone, 4,4-dibutyl-5-pentyl-3-isooxazolidinone, 4-niethyltetrahydro-1,3-oxazin-2-one, 4,6-diethyltetrahydro 1,3-oxazin-2-one, 4,5,6,6-tetramethy1tet-' rahydro-1,3-oxazin-2-one, 4,5,5,6-tetraethyltetrahydro-1,3- oxazin 2 one, 5 octyltetrahydro 1,3-oxazin-2-one, 4-
hexyltetrahydro-1,3-oxazin-2-o-ne, o-dod ecyltetrahydro-1,
3-oxaZin-2-one, 4-butyl-5-dodecyltetrahydro-1,3-oxazin-2- one, G-ethyltetrahydro-1,3-oxazin-2-one, S-eyclohexyltetrahydro-1,3-oxazin-2-one, 4,6-dipentyltetrahydro-1,3:oxazin-Z-pne, Z-rnethyltetrahydro-1,4-oxazin-3-one, S-ethyltetrahydro-l,4oxazin-3-one, 2,5-dimethyltetrahydro-l,4r oxazin-3-one, 2,5,G-triethyltetrahydro-1,4-oxazin-3-one, 2,2,5,5,6-pentamethyltetrahydro-1,4-oxazim3-one, 2,5,6, 6- tetraethyltetrahydro-1,4-oxazin-3-one, 2-methyl-5-buty1-6- octyltetrahydro-l,4-oxazin-3-one, 5-decyl-6-butyltetrahydro-1,4-oxazin-3-one, 2-hexyl-6-dodecyltetrahydro-l,4-oxazin-3-one, Z-methyltetrahydro-1,3-oxazin-4-one, 5,5,6, 6- tetraethyltotrahydro-1,3-oxazin-4-one, 2,5,6-triethyltetrahydro-1,3-oxazin-4-one, 5-pentyltetrahydro-1,3-oxazin-4- one, 2,6-dibutyltetrahydro-1,3-oxazin-4-one, 5-dodecyl-6- propyltetrahydro-1,3-oxazin-4-one, 5-tetradecyl-6-butyltetrahydro 1,3 -oxazin-4-one, 5-octadecyltetrahydro-1,3501;- azin-4-one, 4-methyltetrahydro-l,2 oxazin-3-one, 5,6-dimethyltetrahydro-1,2-oxaZin-3-one, 4-'ethyltetrahydro-1,2- oxazin-S-one, 4,4,5,o-tetraethyltetrahydro-1,2-oxazin-3- one, 4,5,6-tripropyltetrahydro-l,2 oxazin-3-one, 5,5 -dibutyltetrahydro-1,2-oxazin-3-one, 4-butyl-5-octyltetrahydro 1,2-oxazin- 3-one, 5-decyl-6-propyltetrahydro-l,2-oxazin 3 one, 4 dodecyl 5 ethyl 6 butyltetrahydro 1,2-oxazin-3-one, S-hexadecyltetrahydro-1,2-oxa- Zin-3-one, S-decyltetrahydro-1,2-oxazin-3-one, 2-oxazolidinthione, 4-oxazolidinthione, 3-isooxazolidinthione, tetrahydro-1,3-0xazin-2-thione, tetrahydro-1,4-oxazin-3-thione, tetrahydro-l,3-oxaZin-4-thione, tetrahydro-l,2-oxazin-3-thione, 4-dimethyl-Z-oxazolidinthione, 4-butyl-5- hexyl-Z-oxazolidinthione, 4-dodecyl-2-oxazolidinthione, 2,2,5,5-tetramethyl-4-oxazolidinthione, 2,2-diethyl-4-oxazolidinthione, 2-propyl-5-pentyl-4 oxazolidinthione, 2- cyclopentyl-4-oxazolidinthione, 2-tetradecyl-4-oxazolidinthione, 4,5 -dipropy1-3-isooxazolidinone, 4-decy1-3-isooxazolidinthione, 4-ethyl-5-hexadecyl-3-isooxazolidinthione, 4,5,6-trimethyltetrahydro-1,3-oxazin-2-thione, 4,5,6- triethyltetrahydro-l,3-oxazin-2-thione, 5-dodecyltetrahydro-l,3-oxazin-2-thione, 4-hexyl-6-octyltetrahydro-1,310);- aZin-Z-thione, S-decyltetrahydro-1,3-oxazin-2-thione, 2,5,
6,6-tetramethyltetrahydro-1,4-oxazin-3-thione, 2-ethyl-5- propyl-6-butyltetrahydro-1,4-oxazin-3-thione, 2-pentyl- 6- decyltetrahydro-l,4-oxazin-3thione, 5-butyl-6-tetradecyltetrahydro-1,4-oxazin-3-thione, 2,2,5,6-tetramethyltetrahydro-l,3-oxazin-4-thione, 2-butyl-6-cyclohexyltetrahydro-,l, 3-oxazin-4-thione, 5-decy1-6-hexyltetrahydro-1,3-oxazin 4- thione, 4,4,6,6-tetramethyltetrahydro-1,2-oxazin-3-thione, 5,S-dibutyltetrahydro-1,2-oxazin-3-thione, 4,5,6-tripentyltetrahydro-1,2-oxazin-3-thione, and 4-propyl-6-pentadecyltetrahydro-1,2-oXazin-3-thione. j
The a,fl-unsaturated compounds employed in this invention correspond to the torrnula in which Q is a hydrogen atom, an alkyl group of one to eight carbon atoms, or the group to be more fully described hereinafter. T may stand for a cyano group, the group CONZ in which Z may stand for a hydrogen atom or an alkyl group of one to four carbon atoms, or the group -COOR. The symbol R represents a monovalent esterifying group of preferably one' to fourteen carbon atoms and, preferably, alkyl groups of one to fourteen carbon atoms, alkoxyalkyl groups of two to fourteen carbon atoms, aralkyl and alkaralkyl groups of seven to fourteen carbon atoms, and cycloalkyl and alkyl'cycloalkyl groups of three to fourteen carbon atoms. The alkyl groups may be straight or branched chains in any of the known spatial configurations. The alkyl groups positioned on cyclic structures may occupy any possible ring location.
Typical of the representations of Q include a hydrogen atom, the groups methyl, ethyl, propyl, butyl, hexyl, and octyl, and the groups CH CH CH(CH )T.
Typical of the groups that may be employed as T include cyano, carbamoyl, methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, butylcarbamoyl, dimethylcarbamoyl, diethylcarbarnoyl, dibutylcarbamoyl, methylethylcarbamoyl, ethylbutylcarbamoyl, propylbutylcarbamoyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, octoxycarbonyl, dodecoxycarbonyl, tetradecoxycarbonyl, bonyl, methoxyethoxycarbonyl, methoxypropoxycarbonyl, methoxybutoxycarbonyl, methoxyoctoxycarbonyl, methoxydecoxycarbonyl, ethoxymethoxycarbonyl, ethoxyethoxycarbonyl, ethoxypropoxycarbonyl, ethoxyoctoxycarbonyl, propoxyethoxycarbonyl, propoxypropoxycarbonyl, propoxypentoxycarbonyl, propoxyheptoxycarbonyl, butoxymethoxycarbonyl, butoxyethoxycarbonyl, butoxybutoxycarbonyl, butoxynonoxycarbonyl,
butoxydecoxycarbonyl, pentoxymethoxycarbonyl, pentoxybutoxycarbonyl, pentoxypentoxycarbonyl, pentoxyhexoxycarbonyl, pentoxyoctoxycarbonyl, hexoxymethoxycarbonyl, hexoxypropoxycarbonyl, hexoxyhexoxycarbonyl, hexoxyoctoxycarbonyl, heptoxymethoxycarbonyl, heptoxybutoxycarbonyl, heptoxyheptoxycarbonyl, octoxymethoxycarbonyl, octoxyethoxycarbonyl, octoxybutoxycarbonyl, octoxyhexoxycarbonyl, benzoxycarbonyl, phenylethoxycarbonyl, phenylbutoxycarbonyl, ethylbenzoxycarbonyl, phenylbutoxycarbonyl, phenylhexoxycarbonyl, phenyloctoxycarbonyl, butylbenzoxycarbonyl, naphthylmethoxycarbonyl, naphthylethoxycarbonyl, naphthylpropoxycarbonyl, naphthylbutoxycarbonyl, cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopent-oxycarbonyl, cyclohexoxycarbonyl, butylcyclopentoxycarbonyl, octylcyclohexoxycarbonyl. cyclopentylheptoxycarbonyl, and cyclohexyloctoxycarbonyl.
Illustrative of the a,fl-unsaturated compounds that may be used as reactants in this invention include acrylonitrile. methacrylonitrile, u-butylacrylonitrile, u-octylacrylonitrile, acrylamide, methacrylamide, u-ethylacrylamide, m-propylacrylamide, a-octylacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylmethacrylamide, N-ethyl-N-propyltnethacrylamide, N-methyl-aethylacrylamide, N-methyl-N-butyl-a-propylacrylamide, N,N-di-(2-ethylhexyl) acrylamide, N,N-dimethyl-uoctylacrylamide, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, tetradecyl acrylate, methyl methacrylate, butyl methacrylate, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, octyl ethacrylate, methyl a-propylacrylate, butyl a-propylacrylate, nonyl a-propylacrylate, methyl a-butylacrylate, propyl a-butylacrylate, heptyl a-butylacrylate, methyl e-hexylacrylate, pentyl a-hexylacrylate, undecyl a-hexylacrylate, butyl a-heptylacrylate, methyl a-octylacrylate, dodecyl u-octylacrylate, methoxyethyl acrylate, methoxydecyl acrylate, ethoxypropyl acrylate, butoxyhexyl acrylate, methoxymethyl methacrylate, propoxydecyl methacrylate, ethoxyethyl ethacrylate, butoxyoctyl ethacrylate, methoxydodecyl tzpropylacrylate, pentoxypentyl a-propylacrylate, methoxybutyl ot-butylacrylate, butoxyhexyl ubutylacrylate, ethoxyheptyl a-pentylacrylate, methoxyoctyl u-hexylacrylate, propoxybutyl a-heptylacrylate, butoxybutyl a-octylacrylate, benzyl acrylate, naphthylmethyl acrylate, phenylethyl methacrylate, naphthylethyl methacrylate, benzyl ethacrylate, naphthylbutyl methoxymethoxycarall) ethacrylate, phenyloctyl a-propylacrylate, naphthylethyl a-butylacrylate, octylphenylethyl a-pentylacrylate, benzyl 0c hexylacrylate, naphthylmethyl 0c heptylacrylate, phenylhexyl a-octylacrylate, cyclohexyl acrylate, cyclopentyl methacrylate, cyclohexyl ethacrylate, cyclobutyl a-octylacrylate, dimethyl m-methylene-u'-methyladipate, methyl hexyl ot-rnethylene-ot-methyladipate, dimethoxyethyl a-methylene-a-methyladipate, hexoxyethyl methyl a-methylene-ot'-methyladipatc, methyl benzyl u-Inethylene-d-methyladipate, dibenzyl a-methylene-e'-methyladipate, methyl cyclohexy a-methylene-a'-methyladipate, dicyclopentyl a-methylene-a'-methyladipate, methyl octylcyclohexyl a methylene a methyladipate, ethyl naphthylethyl a-methylene-M-rnethyladipate, a-methyb ene-a-methyladiponitrile, a methylene a methyladipamide, N,N'-dimethyl ot-rnethylene-a-methyladipamide, N, N'-dibutyLa-methylene-d-methyladipamide, N-butyl- N-methyl-a-methyleneadipamide, N,N,N-tetramethyl-amethylene-u'-methyladipamide, Z-methylene-S-cyanohexanamide, N-methyl-Z-methylene-5-cyanohexanamide, N- methyl-N-butyl-2-methylene-S-cyanohexanamide, N,N- die'thyl-Z-methylene-5-cyanohexanamide, 2-methyl-5-cyano-5-hexenamide, N-methyl-Z-methyl-S-cyano-S-hexenamide, N,N-dimethyl 2 methyl-S-cyano-S-hexenarnide, N methyl N butyl 2 methyl 5 cyano 5 hexenamide, methyl 2-methyl-5-cyano-5-hexenoate, dodecyl Z-methyl-S-cyano-5-hexenoate, butoxyethyl 2-methyl-5- cyano-S-hexenoate, pentoxypentyl 2-methyl-5-cyano-5- hexenoate, benzyl 2-methyl-5-cyano-5-hexenoate, naphthylethyl Z-methyl-S-cyano-5-hexenoate, cyclohexyl 2- methyl-S-cyano-S-hexenoate, methyl Z-methylene-S-cyanohexanoate, octyl 2-methylene-S-cyanohexanoate, methoxyethyl Z-methylene-S-cyanohexanoate, butoxybutyl Z-methylene-5-cyanohexanoate, octylphenylcthyl Z-methylene-5-cyanohexanoate, naphthylbutyl 2-methylene-S-cyanohexanoate, cyclopentyl Z-methylene-S-cyanohexanoate, methyl Z-methyl-S-carbamoyl-S-hexenoate, ethyl Z-methyl-S-mcthylcarbamoyl-S-hexenoate, decyl 2- methyl-S-dimethylcarbamoyl-S-hexenoate, ethoxyethyl 2- methyl-S-methylpropylcarbamoyl 5 hexenoate, octoxybutyl Z-methyI-S-butylcarbamoyl-S-hexenoate, benzyl 2- methyl-S-ethylcarbamoyl-S -hexenoate, cyclohexyl 2- methyl-S-carbamoyl-5-hexenoate, butyl 2-methylene5- carbamoylhexanoate, tetradecyl Z-methyIene-S-carbamoylhexanoate, methoxyhexyl Z-methylene-S-methylcarbatnoylhexanoate, butoxypropyl Z-methylene-S-diethylcarbamoylhexanoate, benzyl .2-methylene-5-methylethylcarbamoylhexanoate, naphthylpropyl Z-methylene-S-propylcarbamoylhexanoate, and cyclopentyl 2-methylene-5- dipropylcarbamoylhexanoate.
The reactants of this invention are compounds that are known or can be made by known methods. The reactants unite on a substantially mole for mole basis.
The products of this invention are made by bringing together at a reacting temperature in the. presence of a strong alkaline catalyst 21 compound having the formula Q. with one having the formula CHFG-T ataxia solvent such as methanol, i ethanol, butanol, benzene, toluene, xylene, dioxane, diethyl'ether, dimethyl ether of ethylene glycol, and the like. At the conclusion of the reaction the solvent is readily removed such as by s ripping, preferably at reduced pressures.
The present reaction is exothermic in nature and it is frequently advantageous to conduct the reaction by first adding all of the predetermined equivalent amount.
of the selected heterocyclic amide reactant to a reaction vessel along with the catalyst and a portion of the predetermined equivalent amount of the o e-unsaturated compound reactant. In some cases, the above mixture requires some heating in order to initiate the reaction, after which a considerable heat of reaction becomes apparent. As the heat of reaction abates, additional portions of the cup-unsaturated compound are introduced into the reaction vessel until all of the predetermined amount has been used. By using the above-described procedure, the present reaction is consistently conducted in an orderly manner. In many instances, it is entirely satisfactory to introduce all of the predetermined amounts of both of the reactants, particularly when the reactants have the higher molecular weights or substituent groups occupying considerable molecular space or both, in which situations a retarding ponderal effect is readily observable.
The time of reaction is not critical. Generally, times of about one-half hour to twenty-four hours are used, as conditions indicate. It is usually advantageous to conduct the present method for about an hour or two after the heat of reaction is finally dissipated. This is to maximize yields. Otherwise, the-reaction may be concluded as one skilled in the art finds desirable.
A strong alkaline catalyst is used to effect the present method. Typical in this respect are alkali metals such as lithium, sodium, and potassium; alkali metal oxides such as lithium oxide, sodium oxide, and potassium oxide; alkali metal lower alkoxides such as lithium butoxide, sodium methoxide, and potassium ethoxide; alkali metal hydrides such as sodium hydride and potassium 'hydride; alkali metal amides such as sodium amide, lithium amide, and potassium amide; alkali metal lower alkyls and alkenyls such as methyl lithium, ethyl sodium, butyl potassium, allyl sodium, and 'butenyl potassium;
phenylalkyl alkali metals such as benzyl sodium, phenylisopropyl potassium, and alkali metal aromatics such as phenyl sodium, phenyl lithium and phenyl potassium, phenyl butyl sodium; Alfin catalysts, which are commercial mixtures of alkali metal alkenyls and alkali metal alkenoxides, such as allyl sodium with' sodium allyloxide and butenyl potassium with sodium butenyloxide; and quaternary ammonium bases such as trimethylbenzylammonium hydroxide and dimethyldibenzylammonium hydroxide and the corresponding alkoxides such as trimethylbenzylammonium butoxide, choline methoxide, and the like.
Yields up to 90% and over are consistently obtained. In some instances if appreciable amounts of impurities are present in the reactants the yields are somewhat reduced. Accordingly, it is preferred to employ reactants of as high a degree of purity as is conveniently and economically feasible.
At the conclusion of the reaction there may be added to the reaction system enough anhydrous mineral acid such as sulfuric, phosphoric, or the like, to neutralize the catalyst. The salt formed may be removed such as by filtration. Otherwise, the reaction system may be washed with water and the aqueous layer separated or decanted when the product is a solid. Any solvent employed may 'be stripped off, preferably under reduced pressure. Unused reactants when present may be Washed out with water or stripped off under reduced. pressure. If the product is a liquid it may be distilled,if desired. .Solid prod ucts may be recrystallized ina conventional mannerfrom a suitable solvent such as hexane, gheptane, benzene, toluene, ethylene dichloride, chloroform, or the like.
While the products of this invention may be quite satisfactorily prepared according to the foregoing discussion, it may be advantageous in some instances, where ester groups are concerned and the desired R group is not lower alkyl, to first prepare the lower alkyl ester product and then make the desired higher molecular weight ester product by transesterification. This modification may :be used, if desired, to transesterify a single ester group or two ester groups, depending of course on the particular prod- .uct contemplated.
. Transesterification may be conducted preferably in the presence of a strongly acidic esterifying catalyst including sulfuric acid, a lower alkanesulfonic acid, such as butanesulfonic acid, and an arylsulfonic acid, such as p-toluenesu-lfonic acid. It is, also, possible to employ a strongly acidic ion-exchange resin, such as a sulfonated polystyrene or sulfonated phenolformaldehyde resin.
Transesterification is preferably conducted at the reflux temperature of the reaction mixture, which is usually in the range of about to 275 0, preferably in the range of about to 225 C. The pressure is adjusted,
when necessary, to conform to the above temperatures.
Also, if desired, small amounts of an inert volatile organic solvent, such as toluene, xylene, or the like, may be used 'to help regulate the reflux temperature. A lower alkanol is distilled olf as the transesterification progresses and the reaction is continued until the theoretical amount is collected.
At the termination of the transesterification, the product is isolated such as by neutralizing the catalyst, filtering, and distilling, preferably under reduced pressure.
The products of this invention have a wide variety of valuable utilities. The lower molecular weight members are excellent solvents for polymers particularly those in which 'acrylonitrile or a vinyl ester is the major component. The liquid members are useful as synthetic lubricants in which instances they consistently exhibit high viscosity indexes, low pour points, and low volatilities. The present products are useful as plasticizers, particularly for polyvinyl chloride. For instance, a mixture of 28 parts of 3 (2-methoxycarbonylethyl)-2-oxazolidinone, 44 parts of polyvinyl chloride, 0.75 part of tribasic lead sulfate, and 0.4 part of stearic acid milled for seven minutes at 325 F. gave a tough, flexible film of good quality. Comparable results are obtained with the other products of this invention. The present products are effective fungicides when applied against Stemphylium sarcinaeforme and especially Monilinia fructicola in concentrations up to 1.0% in an'inert carrier. These products are at the same time non-phytotoxic in concentrations approaching 1% as determined on tomato plants in a standard test. I
The method and compounds of this invention may be more fully understood from the following examples which are offered by way of illustration but not by Way of limitation. 'Parts by weight are used throughout.
Example 1 There are added to a reaction vessel equipped witha stirrer, a thermometer, and a condenser 17.4 parts of 2-oxazolidinone and .25 part of sodium methoxide. There is then added at a rapid rate 17.2 parts of methyl acrylate. After the initial exothermic heat of reaction subsides another 0.25 part portion of sodium methoxide is added. The reaction mixture is heated to reflux (102 C.) and maintained at this temperature for two hours. The reaction mixture is then distilled and the product collected as distillate. The product distil'ls at 147 to C. at 0.05 mm. absolute pressure. The product=hasan r1 value of 1.4665 and is identified as V methylene-ot'-methyladipate,
3-(2-methoxycarbonylethyl)-2-oxazolidinone. The product has the formula Example 2 There are added to a reaction vessel 20.2 parts of tetrahYdIO-IB-OXElZiIl-LOHB and one part of sodium methoxide. There is added over a period of five minutes 25 parts of ethyl acrylate. The reaction mixture is heated to 95 C. and over a period of three hours there are added in four additions one part of sodium methoxide. The temperature is slowly increased to 135 to 140 C. and held at that level for one hour. The catalyst is neutralized with phosphoric acid and the product isolated by distillation. The product is identified as 3-=(2-ethoxycarbonylethyl tetrahydro-l ,3-oxazin-2-one.
In an analogous way using sodium amide as a catalyst there are made 3-(Z-dodecoxycarbonylethyl)-4,6-dimethyltetrahydro-1,3-oxazin-2-one from 4,6-dimethyltetrahydro-l,3-oxazin-2-one and dodecyl acrylate, 4-(2- 'carbamoylethyl) 2,6 diethyltetrahydro 1,4 oxazin- 3-one from 2,6-diethyltetrahydro-1,4-oxazin-3-one and acrylamide, and 2-butyl-3-(2-cyanopropyl)-6-octyltetrahydro-1,3-oxazin-4-one from Z-butyl-6-octyltetrahydro 1,3-oxazin-4-one and methacrylonitrile.
Example 3 Into a reaction vessel there areadded 14.3 parts of 4,4,5,5-tetramethyl-Z-oxazolidinone and 0.25 part of sodium methoxide. Over a 10-minute period there is added 19.2 parts of butyl acrylate. The temperature of the reaction system rises from the exothermic heat of reaction. There is then introduced 0.50 additional part of sodium methoxide in two equal installments 20 minutes apart. The temperature of the reaction mixture is maintained at 105 to 115 C. for three hours. The catalyst is neutralized by the addition of phosphoric acid and the product is isolated by distillation. The product is identified as 3-(Z-butoxycarbonylethyl)-4,4,5,5-tetramethyl-Z-oxazolidinone.
In like. manner, employing'lithiu-m oxide as catalyst there are prepared 3 2-carbamoylpropyl --decyl-2 oxazolidinthione from 5-decyl-4-oxazolidinthione and methacrylamide, 2,5 dimethyl 3 (2,5 dibenzyloxycarbonylhexyl)-tetrahydro-1,3-oxazin-4-thione from 2,5-dimethyltetrahydro-1,3-oxazin-4-thione and dibenzyl-ozand 2-(2-cyanoethyl)-4,5- diethyltetrahydro-1,2-oxazin-3-thione from '4,5-diethyltetrahydro-l,2-oxazin-3-thione and acrylonit'rile.
Example 4 There are introduced into a reaction vessel five parts of 3-isooxazolidinone and 0.25 part of potassium ethoxide. The mixture is heated to 72 C. and ten parts of methyl methacrylate is added over a period of ten minutes causing the temperature to rise. After 30minutes there is then added 0.25 part of potassium ethoxide causing a further temperature rise. When the heat of reaction abates the mixture is heated at 130 to 136 C. for 40 minutes. The catalyst is neutralized by the addition of phosphoric acid and the product is isolated by distillation. The product corresponds to 2(2-methoxycarbonylpropyl -3 -isooxazolidinone.
In an analogous Way using dimethyl dibenzyl am- 8 monium butoxide as catalyst there are made 2-octadecyl- 3 -(2-dimethylcarbamoylethyl)-2-oxazolidinone from 2- octadecyl-Z-oxazolidinone and N,N-dimethylacrylamide, 2 (2 octoxycarbonylpropyl) 5,5 dibutyl- 3,-, isooxazolidinthione from 5,5-dibutyl-3-isooxazolidinthione and octoxymethacrylate, and -3-(2,5-dibutoxybutoxycarbonylhexyl) 5-hexyl-2-oxazolidinone from S-hexyl-Z-oxazolidinone and dibutoxybutyl-e-methylene-a -methyladipate.
C 7 Example 5, 7
There are introduced into a reaction vessel 20.2 parts of tetrahydro-1,3-oxazin-2-one and two parts of potassium butoxide. There isadded 20 parts of diethyl-mmethylene-a,methyladipate over a period of 15 minutes. The reaction mixture is heated to 82 C. and 1.2 parts of potassium butoxide is added. There is then added dropwise 25 parts of diethyl a-methylene-a'-methyladipate and one part of potassium butoxide. The reaction mixture is heated at 98 to 120 C. for two and one-half hours. There are then added 300 parts of toluene and 100 parts of an aqueous 20% solution of sodium carbonate. The reaction mixture is stirred rapidly and the organic layer is separated, Washed with 100 parts of aqueous 10% phosphoric acid, and then washed with 100 parts of water, The organic layer is stripped to 160 C. at 0.1 mm. absolute pressure leaving the product as the residue. The product is identified as 3(2,5-diethoxycarbonylhexyl)-tetrahydro-l,3-oxazin-2-one.
In a similar way using the sodium methoxide catalyst there are made 2-'(2,5-dicarbamoylhexyl)-tetrahydro-l,2- oxazin-S-one from tetra-hydro-1,2-oxazin-3-one and 2- mcthylene S methyladipamide, 3 (2,5 dicy'anohexyl)-4-butyl-5-octyl-2-oxazolidinthione from 4-butyl-5- octyl-Z-oxazolidinthione and Z-methylene-5-n1ethyladiponitrile, and 3-(Z-carbamoyl-S-cyanohexyl)-6,-dirnethyltetrahydro-l,3-oXazin-4-one from 6,6-dimethyltetrah'ydro- 1,3-oxazin-4-one and 2-methylene-5-cyanohexanamide.
Example 6 Into a reaction vessel there are added 47 parts of tetrahydro-1,3-oxazin-2-thione, 200 parts of toluene and three parts of potassium hydride. There is then added dropwise over a period of minutes 30 parts of acrylonitrile at such a rate that the temperature of the reaction mixture, maintained by the exothermic heat of reaction, is kept below C. The reaction mixture is then allowed to stand for one hour. The toluene layer is removed and anhydrous phosphoric acid is added to neutralize the catalyst. The toluene is removed by stripping at reduced pressure and the product is added by distillation at reduced pressure. The product corresponds to 3- (2-cyanoethyl) -tetrahydrol ,3-oxazin-2-thione.
In like manner, there are made Z-(S-dimethylcarbamoyl 2 cyanohexyl) 4,5,5 trimethyltetrahydro- 1,2-oxazin-3-thione from 4,5,S-trimethyltetrahydro-1,2- oxazin-3-thione and N;N-dimethyl-Z-methyl-5-cyano-5- hexanamide, 3-(2-benzyloxycarbonyl-5propylcarbamoylhexyl)-6,6-dipropyltetrahydro-1,3-0xazin-4-one from 6,6- dipropyltetrahydro-l,3-oxazin-4-one and benzyl Z-methylene-S-propylcarbamoylhexanoate, and 4-(2-cyclohexoxycarbonyl 5 cyanohexyl) 6 octyltetrahydro 1,3- oxazin-4-one from 6-octyltetrahydro-l,3-oxazin-4-one and cyclohexyl 2-methylene-5-cyanohexanoate.
Example 7 After two additional hours the catalyst is neutralized with sulfuric acid. The product is isolated by distillation at reduced pressure.
The product corresponds to 4(2- cyanoethyl)-tetrahydro-1,4-oxazin-3-thione.
9 In like manner employing sodium -as a catalyst there are prepared 2 2-cyanoethyl)'-4-octadecyl-3 -is ooxazolidinthione from 4-octadecyl-3-iso-oxazolidinthione and acrylonitrile, 2 tetradecyl 3 (2,5 dioctoxycarbonylhexyl)-4-oxazolidinone from 2 tetradecyl-4-oxazolidinone and dioctyl a-methylene-a-methyladipate, and 2-butyl-4- (2 carbamoylpropyl) 5,6 -dimethyltetrahydro 1,4 oxazin-3-one from 2-butyl-5,fi-dimethyltetrahydro-l,4- o'xazin-3-one and methacrylamide.
Example 8 There are mixed in a reaction vessel 20 parts of 2-butyl-5,S-dimethyltetrahydro-1,3-oXazin-4-one and 20 parts of methyl methacrylate. There is added two parts of sodium methoxide in 0.5 part portions at 10-minute intervals. The reaction mixture is then heated to 112 to 118 C. for three hours. Phosphoric acid is added to neutralize the catalyst. The product'is isolated by distillation at reduced pressure. The compound corresponds to 2 butyl 3 (2 methoxycarbonylpropyl) 5,5 dimethyltetrahydro 1,3-oxazin-4-one.
Similarly, there are prepared 2-hexyl-4-(2-ethoxycarbonylethyl) tetrahydro 1,4 oxazin 3 one from 2- hexyltetrahydro 1,4 oxazin 3 one and ethyl acrylate, 3 (2 butoxycarbonylethyl) 5,5 dibutyl-4-oxazolidinthione from 5,5 dibutyl 4 oxazolidinthione and butyl acrylate, and 2 (2 butoxycarbonylpropyl) octyl- 3 isooxazolidinthione from r 5 octyl 3 isooxazolidinthione and butyl methacrylate.
Example 9 There are added to a reaction flask 2O par-ts of 6-penty1- Example 10 There are charged to a reaction vessel parts of 3-(2-methoxycarbonylethy1) -2-oxazolidinone and 52 parts of Z-ethylhexanol. The solution is heated at reflux until water no longer collects in a Dean-Stark separator attached to the vessel. There is added five parts of sulfuric acid and the water separator is replaced by a column and distilling head. The reaction mixture is held at to 150 C. Methanol is removed until the theoretical amount is collected. The reaction mixture is washed with two -part portions of aqueous 20% sodium carbonate and'lSO parts of water and then dried over anhydrous magnesium sulfate. Two parts of phosphoric acid is added and the mixture is distilled and the product collected at reduced pressure. The product is identified as 3 [2-(2-ethylhexoxy carbonylethyll -2-oxazolidinone.
In a similar way there are prepared 3-(octoxycarbonylethyl)-tetrahydro=1,3-oxazin 2 one, 2-(2'-'dodecoxycarbonylethyl)-3-isooxazolidinone and 4-foctad'ecoxycarbonylethyl)-6-butyltetrahydro-l,4-oxazin-3-thione from the corresponding methyl esters.
genera 10 V I claim: 1. As a new composition of matter, an adduct of the compounds and having the formula,
T-OHOHa atom, the available valencs of said two to three carbon atoms in said L chain being satisfied by members from the group consisting of a hydrogen atom and alkyl groups whose total carbon content is no greater than eighteen, Y is a chalcogen having an atomic weight of 16 to 32, Q is a member from the group consisting of a hydrogen atom, alkyl groups" or one to eightcarbon atoms, and the group -CH CH C H (CH )T, and T is a member from the group consisting o f a cyanogroup, the group CONZ in which Z is a'rnember' from the group consisting of" a hydrogen atom and alkyl groups of one to eight carbon atoms, and the group COOR in which R is a member from the group consisting of alkyl groups of one to fourteen carbon atoms, alkoxyalkyl groups of two to fourteen carbon atoms, aralkyl and alkaralkyl groups of seven to fourteen carbon atoms, and cycloalkyl and alkylcycloalkyl groups of three to fourteen carbon atoms. I v
2. As a new composition of matter, an adduct of '2- oxazolidinone and an alkyl acrylate having the formula,
AIkyI-OOCCH CHQN 0 \C l in which the alkyl portion contains one to fourteen carbon atoms.
3. As a new composition of matter, an adduct of 2- oxazolidinone' and an alkyl alk'acrylate having the for= mula,
in which the alkyl portion contains one to fourteen carbon. atoms, andlthe' alk portion contains one to eight carbon atoms." 7
4. 'As a new composition of matter, an adduct of 2- oxazolidinone'and a dialkyl ot-metliylene' q' methyladipate having the formula,
o-rrrorr foulonr onom li O O-alkyl (3/ portion contains one to fourteen carbon atoms. v
5. As a new composition of matter, an adduct of 2- oxazolidinone and oHl=eioN ml 2ml) I having the formula,
in which m is an integer of one to nine.
6. As a new composition of matter, an adduct of 2-oxazolidinone and CHFCCONH:
(Cm-1H2n-l) having the formula,
Nrno c oncml in which in is an integer of one to nine.
7. As a new composition of matter, 3-(2-methoxycarbonylethyl)-2-oxazolidinone.
8. As a new composition of matter, 4-(2-carbamoy1- ethyl)-2,6-cliethyltetrahydro-1,4-oxazin-3-one.
9. As anew composition .of matter, 3-(2-ethoxycarbonylethyl)-tetrahydro-1,3-oxazin-2-one.
10. As a new composition of matter, 3-(2,5-cliethoxycarb onylhexyl) -tetrahydro-1,3-oxazin-2-one. i
11. As a new composition of matter 3-(2-cyanoethyl)- tetrahydro-1,3-oxazin-2-thione.
12. A method for the preparation of an adduct of the compounds and having the formula in which L is a threeto four-membered divalent chain containing two to three carbon atoms and one oxygen atom, the available valences of said two to three carbon atoms in said L chain being satisfied by members from the group consisting of a hydrogen atom and alkyl groups whose total carbon content is no greater than eighteen, Y is a chalcogen having an atomic weight of 16 to 32, Q is a member from the group consisting of a hydrogen atom, alkyl' groups of one to eight, carbon atoms, and the group -CH CH CH(CH )T, andT is a member from the group consisting of a cyano "group, the group CONZ in which Z is a member from the group consisting of a hydrogen atom and alkyl groups of one to eight carbon atoms, and the group -COOR in which R is a member from the group consisting of alkyl groups of one to fourteen carbon atoms, alkoxyalkyl groups of twoto fourteen carbon atoms, aralkyl and alkaralkyl groups of seven to fourteen carbon atoms, and cycloalkyl and alkylcycloalkyl groups. of three to fourteen carbon atoms, which comprises bringing. together Aikyl-O o o 0 H1 012mg 1) in which the alkyl portion contains one to fourteen carbon atoms, which comprises bringing together at a reacting temperature in the range of about 0 to 200 C. in the presence of a strong alkaline catalyst, 2-oxazolidinone and an alkyl acrylate.
16. A method for the preparation of an adduct of 2- oxazolidinone and an alkyl alkacrylate having the formula and All;
in which the alkyl portioncontains one to fourteen carbon atoms, which comprises bringing together at areacting temperature in the range of about 0 to 200 C. in the presence of a strong alkaline catalyst, 2-oxazolidinone and a dialkyl nt-methylene-d'-methyladipate.
18. A method fort-he preparation of an adduct of 2- oxazol-idinone and GH=G o N (C m-l lm-l) having the formula CNCHCH:N O
(on-ammo) E 19. A method for the preparation of an adduct of 2- oxazolidinone and having the formula in which m is an integer of one to nine, which comprises bringing together at a reacting temperature in the range of about 0 to 200 C. in the presence of a strong alkaline catalyst, 2oxazolidinone and CH9=CCONH2 m-l Zm-l) 20. A method for the preparation of 3-(2-methoxycarbonylethyl)-2-oxazolidinone which comprises bringing together at a reacting temperature in the range of about 0 to 200 C. in the presence of a strong alkaline catalyst, 2-oxazolidinone and methyl acrylate.
21. A method for the preparation of 4-(2-carbamoy1- ethyl)-2,6-diethyltetrahydro-1,4-oxazin-3-one which comprises bringing together at a reacting temperature in the 14 range of about 0 to 200 C. in the presence of a strong alkaline catalyst, 2,6-diethyltetrahydro-l,4-oxazin-3-one and acrylamide.
22. A method for the preparation of 3-(2-ethoxycarbonylethyl)tetrahydro-l,3-oxazin-2-one which comprises bringing together at a reacting temperature in the range of about 0 to 200 C. in the presence of a strong a1- kaline catalyst, tetrahydro- 1,3-oxazin-2-one and ethyl acrylate.
23. A method for the preparation of 3-(2,5-diethoxyc-arbonylhexyl)-tetrahydro-1,3-oxazin-2-one which comprises bringing together at a reacting temperature in the range of about 0 to 200 C. in the presence of a strong alkaline catalyst, tetrahydro-1,3-oxazin-2-one and diethyl a-methylene-a'-methy1adipate.
24. A method for the preparation of 3-(2-cyanoethy1)- tetrahydro-l,3-oxazin-2-thione which comprises bringing together at a reacting temperature in the range of about 0 to 200 C. in the presence of a strong alkaline cata- 20 lyst, tetrahydro-l,3-oxazin-2-thione and acrylonitr-ile.
No references cited.
UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,852,512 September 16,1958
Newman M. Bortnick It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 10, line 69, claim 4, for where read -which; column 11, lines 415 to 49 claim 12, the formula should appear as shown below instead of as in the patent- L T-oHomN J 1 Signed and sealed this 11th day of November 1958.
[SEAL] Attest V KARL AXLINE, ROBERT C. WATSON, Attestz'gy Oyficer. V Gammissz'oner of Patents.

Claims (2)

1. AS A NEW COMPOSITION OF MATTER, AN ADDUCT OF THE COMPOUNDS
9. AS A NEW COMPOSITION OF MATTER, 3-(2-ETHOXYCARBONYLETHYL)-TETRAHYDRO-1,3-OXAZIN-2-ONE.
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