Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters

Definitions

• Octadienyl esters are prepared by reacting butadiene w th carboxylic' acids in the presence of palladium "catalysts, preferably complexed with phosphite or phosphine ligands, and tertiary amines having a basicity constant K greater than as reaction modifiers.
• the tertiary amines also assist in the separation of the products.
• This invention relates to an improved process for making octadienyl esters.
• tertiary aliphatic amines have been investigated and all significantly enhance the "activity of the palladium catalyst.
• effective amines include trime thylamine, triethylamine, triisopropylamine, ftrib'utylamine and .the like; oxygen-substituted tertiary amines, such as N-methylmorpholine, Z-dimethylamino- "ethanol, 2 dimethylaminoethylacetate, 2 diethylaminoethanol, methyldiethanolamine, triethanolamine and 3-dimethylamino-l-propanol; and tertiary diamines, such as N,N,N,N-tetramethyl-1,3 propanediamine, N,N,N',N'-
• the butadiene dimerization and addition reaction of this invention differs from that described in U.S. Pat. No. 3,221,045, not only in that catalytic co-oxidant is not needed in the process of this invention, but also in that the reactions of this invention are carried out under nonoxidizing conditions and no water is produced in the process.
• the reaction of ethylene, oxygen, and acetic acid to produce vinyl acetate may be written as follows:
• Oxygen is not required to support the butadiene dimerization and addition reaction of this invention, but is also deleterious, if
• the starting 1,3-dienes readily form peroxides, as do the octadienyl ester products.
• Such peroxides lead to undesired radical induced polymerization reactions, and resulting low yields, if any, of the desired products.
• Oxygen also has an unfavorable effect on the phosphorus containing ligands, which are often included in the palladium catalyst, leading to the oxidation ofP(IIl) to P(V) yielding phosphine oxides and phosphates which are ineffective in promoting the palladium catalysts.
• the octadienyl esters formed in the process of this invention are primarily 2,7-octadien-l-ol acetate, although small amounts of the secondary acetate, 1,7-octadiene-3-ol acetate, are also formed.
• the primary acetate is readily converted to octanol-l, which is desirable for making dioctyl phthalate, an important plasticizer.
• the secondary acetate can also be converted to the alcohol by hydrogenation and hydrolysis, although secondary alcohols are less desirable for making plasticizers. However, such secondary alcohols can be converted to useful nonionic surfactants by reaction with ethylene oxide.
• tertiary amines as catalyst modifiers has also provided an unexpected benefit in the separation process.
• the volatile products are stripped from the crude reaction mixtur'e, leaving a catalyst residue for recycle to the. reactor.
• the primary ester and the secondary ester would distill together since their boiling points are close together.
• purified primary ester as a residue or as a second distillate,,if there is enough amine present to .can be derived from a palladium compound which is soluble in the reaction mixture or which can-become soluble therein by reaction with one of the components of said mixture.
• Illustrative palladium compounds which may be used include palladium(II) alkanoates, e.g., palladium(II) acetate, palladium(II) propionate, palladium (II) butyrate, palladium(II) hexanoate, and the like; the palladiumfll) cycloalkanecarboxylates, e.g., palladium- (II) cyclohexanecarboxylate, and the like; palladium(II) aryl carboxylates, e.g., palladium(II) benzoate, palladium- (II) monomethyl phthalate and the like; olefin complexes of palladium, 1,5-cyclooctadiene palladium(II) chloride, 1r-allylpalladium acetate, endo-dicyclopentadienepalladium(II)bromide and the like; complexes with
• Palladium complexes can be generated in situ by reaction of such active forms of palladium with species such as allyl bromide (to give ar-allylpalladium bromide) or trihydrocarbyl phosphines.
• the modifiers can be selected from the trihydrocarbyl (th'e trialkyl, triaryl and alkaryl arsines illustrated by substitu tion of As for P in the compounds described above) and the trihydrocarbylphosphites (trialkylphosphites, e. g.,
• phosphite tris(2-ethoxyethyl)phosphite and the like; triarylphosphites, e.g., triphenylphosphite, tri(p-chlorophenyl)phosphite, tri(1 naphthyl)phosphite, triorthotriethylphosphite, tributylphosphite, tri(2 ethylhexyl)- phosphines, for example, or mixtures of phosphines and/ or arsines and/or phosphites.v v v
• U k c Other phosphorus compounds which areiusefulin the reaction are bicyclic phosphites which include compounds of the general formula V in which R can represent a hydrogen; or an alkyl group, such as methyl, ethyl, isopropyl, nonyl, and the like; or an aryl group such as phenyl, tolyl, naphthyl, andthe like;
• phosphites can be visualized as being derived as theprodnets of esterification of phosphorus acid ((HO) P) with triols of the general formula RC (CR' OH) where R is either hydrogen or some carbon containing radical.
• R and R can be hydroxyl, hydrogen, alkyl, aryl, alkyloxy, aryloxy and'the like as illustrated for the R group of the 'bicyclic phosphites described above.
• modifiers may be added to the reaction mixture in quantities such that, the ratio of 'the total number of moles of modifiers of all kinds (whether added as part of the palladium or platinum catalyst or added separately) to palladium or platinum, can vary, for example, from 200:1 and higher and 1:10 and lower, preferably from 100:1 to 1:1, mostly preferably 20:1 to 1:11
• the catalyst is employed in catalytically significant quantities.
• a palladium concentration in the range from about 0.00000 molar and lower to about 1 molar and higher is suitable.
• a catalyst concentrationin the range from about 0.0001 to about 0.1- molar is preferred.
• the catalyst is a combination of the activet'ransition metal (e.g., palladium) and a ligand such'ias a For As compound as previously described.
• carboxylic acids are acetic acid, chloroaceticjacid,'propionic acid, butyric acid, isobutyric acid, valeric acid; hexanoic acid, heptanoic acid, dodecanoic acid and the like the cycloalkariecarboxylic acids, v e.g., cyclohexanecarboxylic acidand cyclopentanecarboxylic acid and the like'garomatic'acidssuch as benzoicfacid, naphthoic acid, phenylacetic acid and the phenylene diphosphite, and the like.
• monocarboxylicacids with carbon-carbon" nsaturation such as acr'ylic' acid, butenoic';acid,, oleicfacid,
• undecenoic acid ,cinnamicyacidfisorbic acid, and (the like; half acid esters or half dialkyla'mides' of 'clicarboxylic acids; ;as well .as the dicarboxylic r acids themselves, ,f su ch" as direct use of dibasic,aciils, .suehi as fphthalic provides an interesting .embodiment of the invention in that it is possible to synthesize the dioctadienyl phthalates, which fcan be hydrogenated under mild conditions to give dioctyl phthalates, the desired plasticizers, directly.
• This amine can vary from 50 to 0.1 mole of carboxylic acid per atom of N in the added amine, but the preferred range is 10 moles to 0.3 mole of carboxylic acid per atom of N in the amine.
• the ratio of butadiene to carboxylic acid can vary from the actadienyl esters which has been previously diswidely but the more butadiene present relative to the cussed; In the hydrogenation of the dioctadienyl phthalcarboxylic acid the faster the rate of reaction.
• the ratio ates, the olefinic bonds in the alcohol residue are hydroof butadiene t0 carboxylic acid can vary from 0.01-50 genated much'rnore readily than the aromatic double moles of butadiene per mole of carboxylic acid with a bonds, and the hydrogenation can readily be carried out ratio of 0.2-8.0 moles of butadiene per mole of carboxylic under known conditions using typical hydrogenation cataacid being preferred. lysts,s'uch as Raney nickel.
• butadiene need not be used and instead the In the general reaction, butadiene may be replaced 0.; stream from an olefin plant, the usual feed to a buwith other 1,3-dienes to form substituted octadienyl esters.
• tadiene refinery can be employed in the reaction.
• This C Suitable 1,3-dienes include isoprene, piperylene and 1,3- stream is a mixture of butadiene and butenes with smaller hexadiene. amounts of other hydrocarbons.
• The-reactions of the present invention can be carried ge runs were made 1n a three Prht1 s1Ze Chemco out by charging the carboxylic acid, the amine, the pallaglass reactor *eq pp with a meehahleal r- T dium compound, and the ligand modifier to a suitable presaetarlts were charged were y pa g steam sure vessel and introducing butadiene. Other orders of ad- 40 or hot water through an Internal heatlrlg e911. Thls reae' dition of the reactants are also effective.
• the reaction can tor was also q pp with P tlrbe that sarrlples be carried out at --5 to 200 C.
• reaction temperatures are 20 to 180 and most Identification desirably from to 125.0
• N,N,N',N-tetrameth 1-1.s-butanediamine 1.5 90 7.0 25.7 66.7 0.20 0.15 0. 03 1a N,N,N N-tetramethylethylenediamine 9o 20 52 -13 22 65 0.10 0.10 0. 05 14.
• Example 1 a Yields based on converted butadiene. i Butenyl acetates formed included in this figure.
• Example 1 there 4 Runs made in 3 pt. Chemco glass reactor. Catalyst 2 1111110105 Pd (AcAc)z and 2 moles P1111.
• Example 52 (acrylic acid) To a glass-lined, two-liter, stirred Paar autoclave were charged 270 grams (5.0 moles) of butadiene, 360 grams (5.0 moles) of acrylic acid, 450 grams (4.5 moles) of N-methyl-morpholine, 3.3 grams (11 mmoles) of palladium acetylacetonate, and 3.0 grams (l1 mmoles) of triphenylphosphine. This mixture was maintained at 80- 90 C. for 3.5 hours to yield 1091 grams of liquid product. This exact procedure was repeated to give another 1038 grams of liquid product. The runs were combined and 2 grams of hydroquinone added as an inhibitor. VPC analysis on a 6-ft.
• silicone rubber column indicated the presence of 166 grams of 3-octa-1,7-dienylacrylate and 357 grams of 1-octa-2,7-dienylacrylate representing a total yield of 53 percent.
• the liquid product was then stripped through a molecular still to remove the majority of the product from the catalyst. A residue of 328 grams was left.
• the distillate was charged to a x 18" Vigreux still and a small amount of dimethylglyoxime added and then distilled at reduced pressure to yield 668 grams of a fraction, boiling point: 84-l33/9-3.3 mm., that was a mixture of octadienylacrylates and the N-methylmorpholine salt of acrylic acid.
• the product was diluted with water and extracted with ether and the combined ether layers were washed three times with water. After removal of the ether, the residual material, 154 grams, was distilled at reduced pressure. A fraction, 44 grams, boiling point 4755/0.6 mm. was obtained. VPC analysis indicated that the octadienylacrylate isomers were contaminated, probably by the N-methylmorpholine salt of acrylic acid. After several water washes this material was removed. The octadienylacrylate was distilled yielding a mixture that was 90 percent 3-octa-l,7-dienylacrylate.
• Example 53 (phthalic acid) A mixture of 6.0 grams of butadiene, 3.3 grams of .phthalic acid, 1.4 grams of N,N,N,N-tetramethyl-l,3 butanediamine, milliliters of N,N-dimethylacetamide,
• Example 54 (separation of products by azeotropic distillation) 1A1! overhead product from a stripped reaction mixture analyzed as follows: 5.4% acetic acid, 3.5% octatriene, 16.5% tetramethylbutanediamine, I 18.5% 3-acetoxy-1,7- octadiene (3-OAc) and 56.1% l-acetoXy-ZJ-octadiene l-OAc). This mixture (984 grams) was fractionated using a 4-ft. x 1-in. packed grapenutidistillation column. The distillation is summarized below:
• the products were cleanly sprung from amine and acetic acid by the addition of water.
• the water insoluble products were separated from the water layer, washed again with water and dried over sodium sulfate.
• Process for converting butadinej to octadienyl esters which comprises reacting butadiene under non-oxidizing conditions with a carboxylic acid in the presence of a palladium or platinum catalyst and a tertiary amine having a basicity constant K greater than 10"" and recovering said octadienyl esters from the reaction products, said carboxylic acid being selected from the group consisting of aliphatic and aromatic monoand dicarboxylic acids and the ratio of carboxylic acid to tertiary amine being from 10 moles to 0.3 mole of carboxylic acid per atom of nitrogen in the amine.

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• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 1968
  • 1968-09-04 US US00757485A patent/US3711534A/en not_active Expired - Lifetime
• 1969
  • 1969-08-27 DE DE1943453A patent/DE1943453C3/de not_active Expired
  • 1969-09-01 NL NL6913321A patent/NL6913321A/xx unknown
  • 1969-09-03 GB GB43609/69A patent/GB1274072A/en not_active Expired
  • 1969-09-04 FR FR6930230A patent/FR2017392A1/fr not_active Withdrawn
  • 1969-09-04 BE BE738423D patent/BE738423A/xx unknown

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