Cross-Referβnce to Related Applications.

This is a continuation-in-part of application serial number 07/347 , 096, filed on May 3 , 1989.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to new alkadienyl ethers and a process for making same.

2. Statement of Related Art

It is known in the art that conjugated dienes can telomerize with alcohols to give 1,7- and 2,7-alkadienyl ethers. The following references exemplify extensive patent and other literature that relate to such telomerization reactions and novel compounds prepared by such reactions: U.S. Patent Nos. 3,489,813; 3,499,042; 3,670,032; 3,769,352; 3,792,101; 3,887,627; 3,891,684; 3,923,875; 3,992,456; 4,006,192; 4,142,060; 4,146,738; 4,196,135; 4,219,677; 4,260,750; 4,356,333; 4,417,079; 4,454,333; 4,515,711; 4,522,760; and 4,642,392. British Patent Nos. 1,248,592; 1,248,593; 1,354,507; 2,054,394; and 2,114,974. German Patent Nos. 1,807,491; 2,154,370; and 2,505,180. Japanese Patent Nos. 72,020,604; 47,031,906; 48,039,413; 73,042,606; 73,003,605; 49,031,965; 49,048,613; 9,125,313; 74,046,286; 50,157,301; 51/008,206; 51,142,532; 1,149,206; and 51,007,426. Literature articles: Behr,

531 _Λ

2

Organometallics 5, 514-8 (1986) Jolly, Organometallics 5, 473-81 (1986) Dzhemilev, Zh. Org. Khim. 22 (8), 1591-7 (1986) Gaube, J. Prakt. Chim. 327 (4), 643-8 (1985) Jolly, Organometallics 4, 1945-53 (1985) Bochmann, J. Molec. Catalysis 26, 79-88 (1984) Behr, Aspects of Homogeneous Catalysis 5, 5-58 (1984) Gaube, J. Prakt. Chem. 326, (6) 947-54 (1984) Behr, Chem. Ber. 116, 862-73 (1983) Groult, Tetrahedron 39, (9) 1543-50 (1983) Teranishi, J. Org. Chem. 46, 2356-62 (1981) Dzhemilev, Izv. Akad. Nauk. SSSR, Ser. Khim. 8, 1837-425 (1981) Keim, J. Molec. Catalysis 10, 247-252 (1981) Dzhemilev, Zh. Org. Khim. 16 (6), 1157-61 (1980) Yoshida, Tetr. Letters 21, 3787-90 (1980) Tsuji, Pure & Appl. Chem. 51, 1235-41 (1979) Tsuji, Adv. in Organometallic Chem. 17, 141-93 (1979) Singer, J. Organo et. Chem. 137 (3), 309-14 (1977) Chauvin, Tet. Letters 51, 4559-62 (1975) Chauvin, Bull. Soc. Chim. Fr. 652-6 (1974) Beger, J. Prakt. Chem. 315 (6) , 1067-89 (1973) Baker, Chemical Reviews 73 (5), 503-9 (1973) Tsuji, Accounts Chem. Res. 6 (1), 8-15 (1973) Smutny, Annals N.Y. Acad. Sci. 214, 124-142 (1973) Chauvin, Tetr. Letters 51, 4559-62 (1973) Rose, J. Organometallic Chem. 49, 473-6 (1973) Smutny, ACS, Div. Petr. Chem., Prepn. 14 (2), B100- 11 (1969) Takahashi, Bull. Chem. Soc. Japan 41, 254-5 (1968) Takahashi, Bull. Chem. Soc. Japan 41, 454-60 (1968) Smutny, J. Am. Chem. Soc. 89, 6793-4 (1967) Takahashi, Tetr. Letters (26) , 2451-3 (1967) . There have been no reports in the literature of alkadienyl esters of alkynoic acids or esters or ethers of hydroxy-substituted carboxylic acids. Lactic and tartaric acids are included in a list of preferred carboxylic acids which can be used to make unsaturated esters of carboxylic acids by reacting the acids with a conjugated diene in the presence of a palladium catalyst in U.S. Patent No. 3,746,749. The patent contains no teaching or disclosure of how to make any of the claimed alkadienyl esters and/or ethers of the present invention.

The compounds of the present invention are commercially important materials which are useful as emulsifiers, lubricants, and thickening agents. They are similar to other l-substituted-2,7-alkadienyl ethers and 3- substituted-l,7-alkadienyl ethers disclosed in the prior art. For example, U.S. patent No. 4,006,192 discloses the preparation of the di- and tri-l-(2,7-octadienyl) ethers of tri ethylolpropane; British patent application No. 2,054,394 discloses the preparation of the di-l-(2,7- octadienyl) ether of ethylene glycol; Zh. Org. Khim. 16 (6) , 1157-61 (1980) discloses the preparation of the ono- and di-l-(2,7-octadienyl) ethers of 1,4-butanediol, 1,2- propylene glycol, glycerol, and the mono-l-(2,7-octadienyl) ether of 2-hydroxyethoxyethanol; British patent No. 1,354,507 discloses the preparation of l-(2,7-octadienyl) ether of ethanol; J. Prakt. Chem., 315. 1067-76 (1973) discloses the preparation of l-(2,7-octadienyl) ethers of n-butanol, n-hexanol, n-octanol, n-decanol, and n- dodecanol; Japanese patent No. JP 49,031,965 discloses the mono-l-(2,7-octadienyl) ether of ethylene glycol.

These alkadienyl ethers are most readily prepared by the telomerization of a conjugated alkadiene by alcohols in the presence of palladium catalysts. However, the development of economically practical telomerization processes has not been achieved primarily because of the cost of the palladium catalysts. The prior art contains many examples of attempts to deal with the catalyst cost problem. For example, U.S. patent No. 4,642,392 discloses a catalyst recovery method which employs the use of a high boiling reaction solvent which allows for the distillation of the product telomer leaving behind catalyst solution which can be reused many times with, presumably, minimum palladium loss. Other catalyst recovery methods are disclosed in U.S. patent Nos. 4,454,333; 4,552,760; 4,260,750; 4,219,667; 4,142,060; 4,417,079; 4,356,333; Japanese patent No. 50,157,301; 51,149,206.and British patent No. 2,054,394. All of the above catalyst recovery

schemes require additional process operations which add to the cost of the final product.

The use of low palladium levels in the telomerization of conjugated dienes is disclosed in British patent No. 2,114,974. This patent teaches that when 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol telomerized with butadiene, about a 61% yield of monoether based on butadiene can be realized by using a molar ratio of catalyst/diene equal to about 1/20,600. The patent also discloses that a large stoichiometric excess of diol is also necessary in order to obtain high yields of the desired monoether product. For best yields of monoether, the above patent also teaches that the optimum catalytic effect is obtained by combining the palladium catalyst with a nickel(II) compound and a base such as a quaternary ammonium hydroxide. The patent also discloses a method of removing the palladium catalyst with ion exchange resins from the reaction mixture after the reaction has been completed. The palladium levels are obviously not low enough to preclude the recovery step; an operation which the present invention eliminates. U.S. Patent No. 3,746,749 discloses that octadienyl esters of adipic acid can be prepared in 86% yield by employing a molar ratio of Pd/Acid/Butadiene equal to 1/12,300/56,000 and octadienyl esters of fumaric acid can be prepared in 67% yield by employing a molar ratio of Pd/Acid/Butadiene equal to 1/60,000/28,000. However, these low palladium levels are used in conjunction with from 0.1 to 10 moles of an alkali metal salt of a carboxylic acid/mole of carboxylic acid. The process of the present invention overcomes the disadvantages of the prior art processes by utilizing catalyst amounts low enough to allow it to be economically feasible to permit the catalyst to remain in the final reaction products without the need for recovery. At the same time, the yield of dienyl ether product is high while that of the dimerized diene side product is low at these extremely low catalyst concentrations.

SUMMARY OF THE INVENTION The present invention provides new 1- and 3- substituted alkadienyl ethers useful as surfactants, as emulsifiers, as components for cosmetics, as PVC lubricants and as precursors for polymers. The present invention also provides an economical process for the telomerization of conjugated dienes with alcohols using low levels of palladium catalysts. One aspect of the present invention relates to new compounds of the formula I,II, or III

₆ -0-(A) _k -R ₅ ( M )

R ₁₆ ~( -R ₅ ) ( i n )

wherein R, is -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH ₂ 0-DE, or

-CH ₂ 0-FG wherein DE is

and FG is

_g is -CH ₃ , -CH ₂ OH, -CH ₂ ODE or -CH ₂ OFG, wherein -DE and -FG are defined as above; R-, is -CH ₂ OH or -CH ₂ ODE or -CH ₂ OFG, wherein -DE and -FG are defined as above; R ₄ is -CH ₂ ODE or

-CH ₂ OFG, wherein -DE and -FG are defined as above, subject to the following conditions: (1) when R, is -CH ₂ CH ₃ , and R ₂ and R ₃ are -CH ₂ OH, at least one of R ₇ -R ₁₄ is -CH ₃ , and the remainder of R ₇ -R ₁₄ are hydrogen, (2) when , is -CH ₂ CH ₃ , and

R-. and R ₃ are -CH ₂ ODE or -CH ₂ OFG, wherein -DE and -FG are defined as above, at least one of R ₇ -R ₁₄ is -CH ₃ and the remainder of R ₇ -R ₁ are hydrogen; (3) when R ₁ is -CH ₃ , and R _j and R ₃ are -CH ₂ ODE or -CH ₂ OFG, wherein -DE and -FG are defined as above, at least one of R ₇ -R ₁₄ is -CH ₃ and the remainder of R ₇ -R ₁₄ are hydrogen; (4) when R ₁ is -CH ₃ , and 1^ is -CH ₂ 0H, and R ₃ is -CH ₂ 0DE or -CH ₂ OFG, wherein -DE and -FG are defined as above, at least one of R ₇ ~R ₁ is -CH ₃ and the remainder of R ₇ -R ₁₄ are hydrogen, (5) when R., is -CH ₂ CH ₃ , and

R ₂ is -CH ₂ OH, and R ₃ is -CH ₂ ODE or -CH ₂ OFG, wherein -DE and

-FG are defined as above, at least one of R ₇ -R ₁₄ is -CH ₃ and the remainder of R ₇ -R ₁₄ are hydrogen, (6) when R ₁ is CH ₃ , and R ₂ and ₃ are -CH ₂ 0H, at least one of R ₇ -R ₁₄ is -CH ₃ , and the remainder are hydrogen, (7) when R ₃ is -CH ₂ 0H, _j is -CH ₃ or

-CH ₂ OH, (8) when R. is -CH ₂ ODE or -CH ₂ OFG, R ₃ is -CH ₂ ODE or

-CH ₂ OFG, and R ₂ is -CH ₂ OH or -CH ₂ 0DE or -CH ₂ OFG, wherein -DE and -FG are defined as above; _g is -DE or -FG, wherein -DE and -FG are defined as above; k is an integer having a value of from 0 to about 100 subject to the following conditions which depend upon the value of R ₆ : (a) k is greater than 2, when R ₆ is -CH ₃ or -CH ₂ CH ₃ or (b) k is 1 to

100 when R ₆ is a linear, or branched, saturated, or mono- or poly-unsaturated aliphatic radical having from 3 to 12 carbon atoms or (c) k is 0 to 100, when R ₆ is a linear, or branched, saturated, or mono- or poly-unsaturated aliphatic radical having from 13 to 24 carbon atoms, or (d) k is 1 to

100 when R ₆ is an unsubstituted phenyl radical, or a substituted phenyl radical having one or more alkyl groups having from 1 to about 12 carbon atoms, or (e) k is 0 to

100 when R ₆ is a substituted phenyl radical having one or

more electron-withdrawing substituents selected from the group consisting of -N0 ₂ , -CN, -CHO, -S0 ₃ R ₁₅ , or -C0 ₂ R ₁₅ wherein R ₁₅ is a branched, or linear, saturated, or mono- or poly-unsaturated aliphatic radical having from 1 to 24 carbon atoms; A is -(CH ₂ CH ₂ 0)- or -(CH ₂ CH0)- or -(CH ₂ CH ₂ 0)-(CH ₂ CHO)- ;

CH, CH,

p is an integer having a value of from 1 to 8 subject to the following conditions which depend upon the value of R ₁₆ : (a) p has a value of from 1 to 5 when R ₁₆ is a monosaccharide or reduced monosaccharide having 5 or 6 carbon atoms, (b) p has a value of from 1 to 8 when R ₁₆ is a disaccharide having 12 carbon atoms; (c) when R ₁₆ is H(OCH ₂ CH ₂ ) _∑ or R ₅ (OCH ₂ CH ₂ ) _z p has a value of 1 and z is an integer having a value of from 5 to about 100. The invention also relates to compounds of the formula IV or V

0

II

CH ₃ -(CH ₂ ) _x -C=C-(CH ₂ ) _y -C-0DE _IV

CH ₃ -(CH ₂ ) _χ -C__=C-(CH ₂ ) _y -C-0FG V

wherein -DE and -FG are defined as above and wherein: (a) each of R ₇ -R ₁₄ are hydrogen or (b) up to four of R ₇ -R ₁₄ are -CH ₃ and the remainder of R ₇ -R ₁₄ are hydrogen; x and y are integers each having a value of from 0 to 16 such that x + y = 1 to 16.

The invention further relates to compounds of the formula VI, VII, VIII, or IX

0

HO- -C-0-D

(V I )

HO- -C-0-FG

(V I I )

DE-O-M-C-

(VI M)

FG-O-M-C-OH (IX)

wherein M is

R ₂₀ )- wherein -DE and -FG are defined as above and wherein R ₁₈ is hydrogen or a C.-C-,., alkyl group, R ₁₉ is hydrogen or a C,-C ₂₁ alkyl group, R ₂₀ is a divalent C -C ₂₀ alkyl group or a divalent C^C^ alkenyl group, and wherein (a) each of R ₇ -R ₁₄ are hydrogen or (b) up to four of R ₇ -R ₄ are -CH ₃ and the remainder of R ₇ -R ₁₄ are hydrogen.

In addition, the invention relates to compounds of the formula X, XI, XII, or XIII.

CH ₃

H0-CH ₂ -C-CH ₂ -0-DE

C0 ₂ H

(X)

CH ₃

H0-CH ₂ -C-CH ₂ -0-FG

C0 ₂ H

(X I)

CH

DE-0-CH ₂ -C-CH ₂ -0-DE

C0 ₂ H

(X I I )

CH

FG-0-CH ₂ -C-CH ₂ -0-FG

C0 ₂ H

(XI I I )

wherein DE and FG are defined as above and wherein: (a) each of R ₇ -R ₁₄ are hydrogen or (b) up to four of R ₇ ~R ₁₄ are -CH ₃ and the remainder of R ₇ -R ₁₄ are hydrogen.

The invention also relates to compounds of the formula R ₂₁ -(OR ₅ ) _f

(XIV)

wherein R ₂₁ is an alkyl or alkenyl glucoside and wherein the alkyl or alkenyl group of said alkyl glucoside is comprised of from 1 to about 25 carbon atoms, _j is -DE or -FG, wherein -DE and -FG are defined as above, and f is equal to any integer or non-integer from 1 to 4 and wherein: (a) each of R ₇ -R ₁₄ are hydrogen or (b) up to four of R ₇ -R ₄ are -CH ₃ and the remainder of R ₇ -R ₁₄ are hydrogen.

Still another aspect of the present invention relates to a process for the telomerization of conjugated dienes with monofunctional alcohols comprising the steps of: (1) reacting (a) at least one monofunctional alcohol reactant, and (b) at least one conjugated diene in the presence of a catalyst effective amount of a palladium catalyst, wherein said catalyst is present in a mole ratio of catalyst to diene of up to about 1:10,000, and (2) isolating said telomerization reaction product from said reaction mixture.

Yet another aspect of the present invention relates to a process for the telomerization of conjugated dienes with polyols comprising the steps of: (1) reacting in a reaction mixture, (a) at least one polyol reactant having at least one -CH ₂ OH group, (b) at least one conjugated diene, in the presence of a catalyst effective amount of a palladium catalyst, wherein said catalyst is present in a mole ratio of catalyst to diene of up to about 1:5,000, and wherein when said reaction mixture is non-homogeneous or when said polyol reactant contains two -CH ₂ 0H groups separated by at least two carbon atoms, adding to said reaction mixture from about 10% to about 50% by weight of least one saturated aliphatic secondary or tertiary alcohol solvent, and (2) isolating the telomerization reaction product from said reaction mixture.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".

It is understood that formulas I through XIII encompass all possible stereoisomers and are not meant to depict any particular stereoisomer of the 1- and 3- substituted alkadienyl ethers or esters represented thereby. Because the compounds of the present invention are conveniently and preferably made by telomerization of a conjugated diene with an appropriate telogen, the present invention contemplates all the various structural and diastereoisomers that can be formed by telomerizing a conjugated diene or a mixture of conjugated dienes with compounds having alcohol and/or carboxylic acid functionalities. For example, the product of the telomerization of 1,3-butadiene may contain a mixture of cis and trans and other diasteriomeric l-substituted-2,7- octadienyl ether and 3-substituted-l,7-octadienyl ether (R ₇ to are hydrogen) . Each product of the telomerization of piperylene and isoprene can contain a total of 16 compounds because each diene can dimerize in 4 different ways (head- to-head, head-to-tail, tail-to-head, tail-to-tail) and each of the possible dimers can either be 1- or 3-substituted. Cis and trans isomers of each of the 16 possible compounds can also be formed in the telomerizations of isoprene and piperylene. In another example, the product of the telomerization of a mixture of 1,3-butadiene and piperylene (1,3-pentadiene) will include the products of the head-to- head, head-to-tail, tail-to-head, tail-to-tail codi erization of the two dienes. The products of the codimerization are the l-substituted-2,7-nonadienyl ether (R ₁₄ = CH ₃ , R ₇ -R ₁₃ = H) , 5-methyl-2,7-octadienyl ether (R„ = CH ₃ , R ₇ -R ₁₀ = R ₁₂ -R _ι4 ^{= H} ) i l-methyl-2,7-octadienyl ether (R ₇ = CH ₃ , R ₈ -R ₁ = H) , 4-methyl-2,7-octadienyl ether (R ₁₀ - CH ₃ , R ₇ -R = R ₁₁ -R ₁₄ = H) and the 3-substituted isomers thereof along with the 1- and 3-substituted homodimerization products and all of the stereoisomers of the above.

3531

12

The compounds of the present invention fall into the general classifications of 1- and 3-substituted alkadienyl ethers and esters. The 1- and 3-substituted alkadienyl ethers and esters of the present invention can be made by any method of making ethers or esters known to those skilled in the art. The preferred method of preparing the 1-and 3-substituted alkadienyl ethers and esters of the present invention is through the telomerization of 1,3- alkadienes with compounds having alcohol and/or carboxylic acid functionalities (telogens) . Such alkadienes can be branched- or straight-chain aliphatic conjugated dienes having from 4 to 20 carbon atoms, which may optionally be substituted with one or more inert groups such as ^-C ₈ alkyl groups, phenyl, cyclohexyl, nitro, oxo, alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl group, or halogen such as fluorine or chlorine wherein the halogen is in a position inert to the reaction conditions, for example, chloroprene. Other conjugated dienes that can be used to make the compounds of the present include 1,3- butadiene, dimethylbutadiene, isoprene (2-methyl-l,3- butadiene) , piperylene (1,3-pentadiene) , 1,3-hexadiene, 2,4-hexadiene, chloroprene, 1-cyclohexyl-l,3-butadiene, 1-phenyl-l,3-butadiene, 2,4-octadiene, 3-methylpiperylene, 2-methyl-2,4-pentadiene, 1,3-cyclohexadiene, and 1,3- cyclooctadiene. The preferred conjugated dienes are 1,3- butadiene, dimethylbutadiene, isoprene, and piperylene. The most preferred conjugated diene is 1,3-butadiene.

Preferably, the alkadienyl ethers of the formulas I, II, or III can be made by telomerizing one or more conjugated dienes with a compound having one or more alcohol functionalities such as simple alcohols, polyalkylene glycols, phenols, sugars, and hydroxy- subtituted carboxylic acids. Alcohols that can be used to make the compounds of the present invention .are polyols such as neopentyl glycol (2,2-dimethyl-l,3-propanediol) , trimethylolethane [2-methyl-2-(hydroxymethyl)-1,3-

propanediol] , trimethylolpropane [2-ethyl-2- (hydroxymethyl)-l,3-propanediol] , and pentaerythritol. Polyalkoxylated aliphatic alcohols having from 3 to 24 carbon atoms that are linear, or branched, saturated, or mono- or poly-unsaturated can also be used. Examples of such polyalkoxylated alcohols include polyethoxylated, polypropoxylated, and polyethoxylated-propoxylated butanols, hexanols, octanols, deσanols, and dodecanols. Also included are polyalkoxylated methanol and ethanol in which the degree of polymerization is greater than 2. Also included in this group are aliphatic alcohols having from 13 to 24 carbon atoms that are linear, or branched, saturated, or mono- or poly-unsaturated. Polyethyleneglycols having a degree of polymerization equal to or greater than 5 can also be used. The alcohols that can be used to make the compounds of the present invention can also be aromatic. For example, phenols having one or more electron-withdrawing substituents selected from the group consisting of -N0 ₂ , -CN, -CHO, -S0 ₃ R ₁₅ , or -C0 ₂ R ₁₅ wherein R ₁₅ is a branched, or linear, saturated, or mono- or poly-unsaturated aliphatic radical having from 1 to 24 carbon atoms can also be used. Such phenols include salicylaldehyde, m-hydroxybenzaldehyde , p- hydroxybenzaldehyde, methyl 4-hydroxybenzoate, methyl 2- hydroxybenzoate (methyl salicylate) , o-, m-, p-nitrophenol, o-, m-, p-cyanophenol (o-, m-, p-benzonitrile) , o-, m-, p-hydroxybenzenesulfonic acid, and 2,6-dinitrophenol. Alkoxylated derivatives of phenols can also be used to make the compounds of the present invention. Such alkoxylated phenols include those which are ethoxylated, propoxylated, or ethoxylated and propoxylated with from 1 to 100 moles of ethylene oxide, propylene oxide, or a combination of ethylene oxide and propylene oxide. Examples include ethoxylated nonylphenol and ethoxylated octylphenol. Sugars can also be used to make the compounds of the present invention. Such sugars include monosaccharides

having 5 or 6 carbon atoms such as any of the common 5 carbon sugars including for example, ribose, arabinose, xylose, lyxose or any of the common 6 carbon sugars such as allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fructose, sorbose. Sugar derivatives such as sorbitol, and N-methylglucamine can also be used as can disaccharides having 12 carbon atoms such as any of the common 12 carbon disaccharides including sucrose, maltose, cellobiose, lactose, isomaltose. Compounds of the formula XIV are alkadienyl ethers of an alkyl or alkenyl glucoside having the formula XV

XV wherein R^ is an alkyl or alkenyl group having from 1 to 25 carbon atoms. The preferred glucosides are methyl, butyl, and oleyl wherein R ₂₂ in formula XV is methyl, butyl and oleyl respectively. The alkadienyl ethers of the alkyl glucosides are etherified at the 2, 3, 4, or 6 hydroxyl groups depending upon the degree of etherification. For example, a mono alkadienyl ether of a glucoside of formula XIV can be etherified at either the 2, 3, 4, or 6 OH. A di alkadienyl ether can be etherified at any combination of two of the 2, 3, 4, or 6 OH. Because f in formula XIV represents an average value of the degree of etherification, it can have any integer or non-integer value from 1.0 to about 4.0. For example, the degree of etherification of a sample of alkadienyl ether of an alkyl or alkenyl glucoside containing 2 moles of alkadiene per mole of glucoside may be composed of compounds having a

degree of etherification of from 1 to 4. The average degree of etherification in that case would be equal to 2.0. The preferred alkadienyl ethers of the glucosides of formula XIV are the mono-, di-, tri-, and tetra-octadienyl ethers of methyl glucoside, the mono-, di-, tri-, and tetra- alkadienyl ethers of n-butyl glucoside, the mono-, di-, tri-, and tetraalkadienyl ethers of oleyl glucoside. The most preferred alkadienyl ethers of the glucosides of formula XIV are the octadienyl ethers of methyl, butyl, and oleyl glucosides having an average degree of etherification of from about 1.6 to about 2.4. Also preferred are the octadienyl ethers of commercially available glucosides which are mixtures C ₈ -C _1C alkyl glucosides wherein R ₂₂ in formula XV is a C _β -C _1fJ alkyl group, mixtures of C ₁₂ -C ₁₄ alkyl glucosides wherein R ₂₂ in formula XV is a C ₁₂ -C ₁₄ alkyl group, and mixtures of C _l2 -C ₁₃ branched alkyl glucosides wherein ^ in formula XV is a C ₁₂ -C ₁₃ alkyl group. These commercially available mixtures also can contain non-glucose materials such as maltosides, and di- and tri-carbohydrate derivatives.

Preferred compounds of the formula I can be made by reacting 1,3-butadiene, dimethylbutadiene, piperylene, or isoprene or a combination of such dienes with (a) neopentyl glycol (2 , 2-dimethyl-1 , 3-propanediol ) (b) tri ethylolpropane [2-ethyl-2-(hydroxymethyl)-1,3- propanediol] (c) trimethylolethane [2-methyl-2- hydroxymethyl)-1,3-propanediol] or (d) pentaerythritol.

Preferred compounds of formula II can be made by reacting 1,3-butadiene, piperylene, or isoprene with (a) CH ₃ (OCH ₂ CH ₂ ) ₄ . ₁₀₀ - or CH ₃ CH ₂ (OCH ₂ CH ₂ ) ₄ . ₁₀₀ - , (b) C ₃ -C ₁₂ aliphatic branched or linear, saturated or mono- or poly- unsaturated alcohols which have been alkoxylated with from 1 to about 100 moles of ethylene oxide, propylene oxide, or ethylene and propylene oxides wherein the ethylene/propylene ratio is from about 2/1 to about 1/2,

(c) C ₁₃ -C ₂₄ aliphatic branched or linear, saturated or mono-

3531

16 or poly-unsaturated alcohols which have been alkoxylated with from 0 to about 100 moles of ethylene oxide, propylene oxide, or ethylene and propylene oxides wherein the ethylene/propylene ratio is from about 2/1 to about 1/2, (d) substituted or unsubstituted phenols such as mono- and dinonyl phenol, mono- and dioctyl phenol which have been alkoxylated with from 1 to about 100 moles of ethylene oxide, propylene oxide, or ethylene and propylene oxides wherein the ethylene/propylene ratio is from about 2/1 to about 1/2, or (e) phenols having one or more electron- withdrawing substituents selected from the group consisting of -N0 ₂ , -CN, -CHO, -S0 ₃ R ₁₅ , or -C0 ₂ R ₁₅ wherein R ₁₅ is a branched, or linear, saturated, or mono- or poly- unsaturated aliphatic radical having from 1 to 24 carbon atoms. The preferred phenols are salicylaldehyde, methyl p- hydroxybenzoate, methyl salicylate, and the polyethoxylates and polypropoxylates of mono- and di-nonylphenol, mono- and di-octylphenol that have been alkoxylated with from 1 to about 100 moles of ethylene oxide, propylene oxide, or ethylene and propylene oxides wherein the ethylene/propylene ratio is from about 2/1 to about 1/2.

One set of preferred compounds of formula III can be made by reacting 1,3-butadiene, piperylene, or isoprene with a monosaccharide having 5 or 6 carbon atoms such as any of the common 5 carbon sugars including but not limited to ribose, arabinose, xylose, lyxose or any of the common 6 carbon sugars including but not limited to allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fructose, sorbose. Sugar derivatives such as sorbitol, and N-methylglucamine can also be used. Disaccharides having 12 carbon atoms such as any of the common 12 carbon disaccharides including but not limited to sucrose, maltose, cellobiose, lactose, isomaltose can also be used. The number of OH functionalities etherified on each sugar formula unit (defined as the degree of etherification) in any of the above sugars varies with the

17 amount of diene used and reaction parameters such as time and temperature. Therefore, the degree of etherification can vary from 1 (for 1 OH etherified in a mono- or disaccharide) to 8 (for a totally etherified 12 carbon disaccharide) . Therefore, the value of the subscript p in formula III when R ₁₆ is a mono- or disaccharide or a sugar derivative such as sorbitol or N-methylglucamine can vary from l to 8.

Another set of preferred compounds of formula III can be made by reacting one mole of 1,3-butadiene, piperylene, or isoprene with one mole of a polyethylene glycol having a degree of polymerization of from 5 to about 100 to for a monoether (p=l) or two moles of 1,3-butadiene, piperylene, or isoprene with one mole of a polyethylene glycol having a degree of polymerization of from 5 to about 100 to form a diether (p = 2) .

The preferred compounds of formula IV and V are those- in which x=7 and y=7 and (a) each of R ₇ -R ₁₄ are hydrogen or (b) up to four of R ₇ -R ₁₄ are -CH ₃ and the remainder of R ₇ -R ₁₄ are hydrogen. Compounds the formula IV or V can be made by telomerization of 1,3-butadiene, dimethylbutadiene, isoprene (2-methyl-l,3-butadiene) , piperylene (1,3- pentadiene) using [Pd(acac) ₂ ]/tri(o-tolyl)phosphitecatalyst in isopropanol at 50°C. Alkadienyl esters of 2-alkynoic acids (in cases where y=0 in formulas IV and V) are best prepared by means other than telomerization of a conjugated diene with a 2-alkynoic acid. Attempts to telomerize a conjugated diene with the a 2-alkynoic acid results in the formation of a cyclohexadiene derivative as the major product instead of the desired octadienyl ester. Alkadienyl esters of formulas IV and V wherein y*=0 can be prepared by any esterification method known to those skilled in the art. For example, the direct esterification of a 2-alkynoic acid with either 1,7-octadien-l-ol or l,7-octadien-3-ol or the transesterification of a alkynoate ester with either 1,7-octadien-l-ol or l,7-octadien-3-ol can be used. The

531

18

1,7-octadien-l-ol and/or l,7-octadien-3-ol can be obtained directly by telomerization of a 1,3-diene with water in the presence of carbon dioxide as described in Aspects of Homogeneous Catalysis, 5., 24 (1984) or indirectly by for example, hydrolysis of an alkanoate ester of either 1,7- octadien-1-ol or l,7-octadien-3-ol prepared by telomerization of a 1,3-diene with a simple alkanoic acid such as acetic acid as disclosed in U.S. patent No. 3,746,749. The preferred 1-and 3-substituted alkadienyl esters and ethers of hydroxy-substituted carboxylic acids have the formulas VI, VII, VIII, and IX are those in which R ₁₈ is hydrogen or methyl, and wherein R ₁₉ is CH ₃ -(CH ₂ ) ₅ - and R ₂₀ is -CH ₂ -CH=CH-(CH ₂ ) ₇ -. The preferred mono- and di- 1- and 3-substituted alkadienyl ethers of 2,2-dimethylolpropionic acid are those in which: (a) each of R ₇ -R ₁₄ are hydrogen or (b) up to four of R ₇ -R ₁₄ are -CH ₃ and the remainder of R ₇ -R ₁₄ are hydrogen in formulas X, XI, XII, and XIII. These compounds can be made by telomerization of 1,3-butadiene, dimethylbutadiene, isoprene (2-methyl-l,3-butadiene) , piperylene (1,3- pentadiene) using [Pd(acac) ₂ ]/triphenylphosphine catalystin isopropanol at 70°C.

The preferred alkadienyl ethers of the compounds of formula XIV are the mono-, di-, tri-, and tetraoctadienyl ethers of methyl glucoside wherein R^ is methyl glucoside and f is 1, 2, 3 or 4 in Figure XIV; the mono-, di-, tri-, and tetraalkadienyl ethers of n-butyl glucoside wherein R^ is n-butyl glucoside and f is 1, 2, 3 or 4 in Figure XIV; the mono-, di-, tri-, and tetraalkadienyl ethers of oleyl glucoside wherein R ₂₁ is oleyl glucoside and f is 1, 2, 3 or 4 in Figure XIV.

The process of the present invention rests on the discovery that conjugated dienes can be telomerized with alcohols to form l-substituted dienyl ethers in high yields in the presence of very low levels of palladium catalyst.

In cases where the alcohol reactant is a polyol having two -CH ₂ OH groups separated by more than one carbon atom or where the alcohol reactant, whether mono- or polyfunctional, is not soluble in the reaction mixture, from about 10% to about 50% by weight of at least one saturated aliphatic secondary or tertiary alcohol must be added to the reaction mixture in order for the low levels of palladium catalyst to be effective in producing high yields of the desired alkadienyl ether products. In the telomerization processes of the prior art relatively large concentrations of palladium catalysts are required in order to realize practical yields of product. Since the catalysts are so expensive, they have to be recovered in order to make the processes economically viable. Because these recovery operations add to the costs of the telomerization processes, the commercial production of dienyl ethers has not been widespread. The process of the present invention eliminates the need for using prohibitively high palladium catalyst levels and for costly catalyst recovery operations. The process of the present invention is a method of telomerizing conjugated dienes with alcohols in the presence of very low levels of palladium catalyst relative to the amount of diene used in the reaction. The process of the present invention is carried out by reacting one or more monofunctional alcohol reagents and/or one or more polyols with one or more conjugated dienes in the presence of a catalyst effective amount of a palladium catalyst. The amount of catalyst is a function of the amount of conjugated diene and is expressed as the molar ratio of catalyst: iene. The effective amount of catalyst of the present invention is in the range of from 1:5,000 to about 1:150,000, and preferably from 1:25,000 to 1:75,000.

The monofunctional alcohols which can be employed in the process of the present invention include primary monools, i.e., alcohols of the formula RCH ₂ OH wherein R is

hydrogen, a straight- or branched-chain alkyl, alkenyl or alkadienyl group having from 1 to 8 carbon atoms. It is preferred that R be a straight- or branched-chain alkyl having from 1 to 8 carbon atoms. Examples of the monools of the formula RCH ₂ OH where R is hydrogen, a straight-chain alkyl include methanol, ethanol, 1-propanol, 1-butanol, 1- pentanol, 1-hexanol, 1-heptanol, and 1-octanol. Examples of the monools of the formula RCH ₂ OH where R is a branched- chain alkyl group include 2-methyl-l-propanol, 2,2- dimethyl-1-propanol, 2-methy1-1-butanol, 3-methyl-l- butanol, 3,3-dimethyl-l-butanol, 2-methyl-l-pentanol, 3- methyl-1-pentanol, 4-methyl-l-pentanol, and the like.

Examples of the monools of the formula RCH ₂ 0H where R is an alkenyl or alkadienyl group having from 1 to 8 carbon atoms include 2-propenol, 2-buten-l-ol, 3-buten-l-ol, 2- methyl-2-propen-l-ol, 2-penten-l-ol, 3-penten-l-ol, 4- penten-1-ol, 2-hexen-l-ol, 3-hexen-l-ol, 4-hexen-l-ol, 5- hexen-1-ol, 2,4-pentadien-l-ol, 2,4-hexadien-l-ol, 3,5- hexadien-1-ol, and the like. The monofunctional alcohols also include substituted phenols such mono- and dinonyl phenol and mono- and dioctyl phenol, and phenols having one or more substituents selected from the group consisting of -N0 ₂ , -CN, -CHO, -S0 ₃ R ₁₅ , or -C0 ₂ R ₁₅ wherein R ₁₅ is a branched, or linear, saturated, or mono- or poly-unsaturated aliphatic radical having from 1 to 24 carbon atoms can also be used. Such phenols include salicylaldehyde, m-hydroxybenzaldehyde, p- hydroxybenzaldehyde, methyl 4-hydroxybenzoate, methyl 2- hydroxybenzoate (methyl salicylate) , o-, m-, p-nitrophenol, o-, -, p-cyanophenol (o-, m-, p-benzonitrile) , o-, -, p- hydroxybenzenesulfonic acid, and 2,6-dinitrophenol. Alkoxylated derivatives of the phenols described above can also be used to make the compounds of the present invention. Such alkoxylated phenols include those which are ethoxylated, propoxylated, or ethoxylated and propoxylated with from 1 to 100 moles of ethylene oxide, propylene

oxide, or a combination of ethylene oxide and propylene oxide.

The polyols which can be employed in the process of the present invention include compounds of the formula HOR'CH ₂ OH wherein R' is a straight or branched-chain alkyl group having from 1 to 11 carbon atoms. It is preferred that R be an alkyl or branched alkyl group having from 1 to

3 carbon atoms. Other polyols which are employed in the process of the present invention are compounds of the formula HOCH ₂ -R ² -CH ₂ OH where in R ² is CHOH, C(CH ₃ ) ₂ or C(CH ₂ OH) ₂ .

Examples of the polyols of the formula HOR ² CH ₂ OH where R ² is a straight or branched-chain alkyl group having from 1 to 11 carbon atoms include ethylene glycol, 1,2- propanediol, 1,3-propanediol, 1,2-butanediol, 1,3- butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- hexanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl- 1,2-propanediol, and the like. The preferred polyol in these cases is 1,2-propanediol. Examples of the polyols of the formula HOCH ₂ -R ² -CH ₂ OH where in R ² is CHOH, C(CH ₃ ) ₂ or C(CH ₂ CH ₃ ) (CH ₂ OH) include 2, 2-dimethyl-l, 3-propanediol, glycerol (1,2,3- propanetriol) , 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, and the like. The preferred polyol in these cases is glycerol.

The conjugated dienes that can be employed in the process of the present invention include branched- or straight-chain aliphatic conjugated dienes containing from

4 to 20 carbon atoms, or cyclic dienes containing from 6 to 8 carbon atoms, and which may optionally be substituted with one or more inert groups such as C_.-C ₈ alkyl groups, phenyl, cyclohexyl, nitro, oxo, alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl group, or halogen such as fluorine or chlorine wherein the halogen is in a position inert to the process conditions, for example, chloroprene. Other conjugated dienes that can be used in the process of

this invention include 1,3-butadiene, dimethylbutadiene, isoprene, piperylene, 1,3-hexadiene, 2,4-hexadiene, chloroprene, 1-cyclohexyl-l,3-butadiene, l-phenyl-1,3- butadiene, 2,4-octadiene, piperylene, 2-methyl-2,4- pentadiene, 1,3-cyclohexadiene, and 1,3-cyclooctadiene. The preferred conjugated diene is 1,3-butadiene.

When the process of the present invention is carried out in cases where the alcohol reactant is a polyol having two -CH ₂ OH groups separated by at least two carbon atoms, or in cases where the alcohol reactant, whether mono- or polyfunctional, is not soluble in the reaction mixture, it is necessary to add from about 10% to about 50% by weight of at least one saturated aliphatic secondary or tertiary alcohol solvent in order for the low levels of palladium(II) catalyst to be effective in producing high yields of the desired alkadienyl ether products. The secondary or tertiary alcohol solvents are saturated aliphatic alcohols having from 3 to 10 carbon atoms preferably 3 to 4 carbon atoms. The secondary or tertiary alcohol solvents can also contain a primary alcohol group in addition to a secondary or tertiary alcohol group. For example, 1,2-propanediol could be used as the solvent because it contains a secondary alcohol group in addition to the primary alcohol group. The preferred secondary alcohol solvents are isopropyl alcohol (2-propanol) and 1,2-propanediol. The preferred tertiary alcohol solvent is t-butyl alcohol (2-methyl-2-propanol) . Mixtures of two or more of such secondary and/or tertiary alcohol solvents can also be used. The ratio of alcohol reactant to conjugated diene reactant is preferably about two moles of diene per mole of alcohol functionality present in the alcohol. However, if desired, ratios of alcohol equivalents to conjugated diene equivalents of from 0.8-1.5 to 1 can also be employed, or even using a greater excess of alcohol or conjugated diene, but the most advantageous and economical embodiment of the

process is when the reactants are approximately equivalent. The catalyst used in the process is a catalyst system comprised of a palladium compound and a cocatalyst. The palladium catalysts are selected from the group consisting of palladium acetylacetonate [Pd(acac) ₂ ], bis(allyl)palladium [Pd(C _j H ₅ ) ₂ ], bis(cyclooctadiene)palladium [Pd(C0D) ₂ ], palladium chloride (PdCl ₂ ) , palladium acetate [Pd(0Ac) ₂ ], and allyl palladium chloride [Pd(C ₃ H ₅ )Cl] . The cocatalysts are selected from the group consisting of trialkylphosphine, triarylphosphine, or triarylphosphite. A mixture of alkyl, aryl, or aryl/alkyl phosphines and phosphites can also be used. Examples of trialkylphosphines include triethylphosphine and tributylphosphine. Examples of triarylphosphines include triphenylphosphine, o-,m-,p- tolylphosphine, l,2-bis(diphenylphosphino)ethane, and 1,2- bis (di-p-tolylphosphino) ethane. Examples of triarylphosphites include tri (o-tolyl)phosphite, triphenylphosphite, trimethylphosphite, and triethylphosphite. Another suitable catalyst is tetrakis(triphenylphosphine)palladium [Pd(PPh ₃ ) ₄ ].

The most preferred catalyst systems are complexes of the acetylacetonate of Pd(II) with two equivalents of triphenylphosphine as a ligand, palladium(II) acetate with two equivalents of triphenylphosphine as a ligand, palladium(II) chloride with two equivalents of tr iphenylphosphine as a ligand, and tetrakis(triphenylphosphine)palladium.

The mole ratio of catalyst to conjugated diene in cases where a monofunctional alcohol is the telogen is from about 1:150,000 to about 1:10,000. The mole ratio of catalyst to conjugated diene in cases where a polyol is the telogen is from about 1:150,000 to about 1:5,000. The preferred amount is from about 1:150,000 to about 1:25,000.

The reaction is achieved without the addition of a catalyst reductant such as triethylaluminum or sodium borohydride, which are often used in the prior art

processes. The catalyst used herein is preferably prepared by combining a palladium catalyst with two equivalents of a cocatalyst in the alcohol reactant to be used in the process. The conjugated diene is then added to the above to form a reaction mixture. If the reaction mixture is non- homogeneous or if the alcohol reactant is a polyol having two -CH ₂ OH groups separated by at least two carbon atoms, then from about 10% to about 50% by weight of least one saturated aliphatic secondary or tertiary alcohol solvent is added reaction mixture. The preferred amount of the saturated aliphatic secondary or tertiary alcohol solvent to be added must be determined on an individual basis.

The synthesis of the compounds of the present invention as well as the process of the present invention are carried out in any suitable reaction vessel, such as a glass autoclave, steel autoclave, or any other reaction vessel equipped for reactions under pressure.

The reaction temperatures are in the range of from 40°C to 100°C preferably in the range of from 60°C to 80°C. The general procedure for the synthesis of the compounds of the present invention as well as the process of the present invention involves introducing the palladium catalyst-alcohol reactant solution into a reaction vessel along with any necessary saturated aliphatic secondary or tertiary alcohol solvent or mixtures thereof, followed by addition of the diene. The reaction mixture is heated slowly to a reaction temperature of 40°C to 100°C and the reaction is carried out for a period of from 5 to 15 hours. Alternatively, the conjugated diene can be added in increments to the other reaction mixture components after they have been heated to reaction temperature.

The reaction products are isolated by standard techniques such as distillation, crystallization or filtration. The following examples are meant to illustrate but not limit the invention.

Example 1. Telomerization of 1.3-butadiene with 1.2- propanediol.

To a 400 ml glass autoclave equipped with a magnetic stir bar, there was added 0.0038 grams (0.0125 mmol) of palladium(II) acetylacetonate, 0.0066 grams (0.025 mmol) of triphenylphosphine, and 47.6 grams (625 mmol) of 1,2- propanediol. The autoclave was connected to a pressure gauge and the assembly was weighed. The autoclave assembly was evacuated and flushed three times with argon after which 70.9 grams (1313 mmol) of 1,3-butadiene was added with a syringe. The autoclave was then reweighed, heated to 70°C and maintained at that temperature for 12 hours while stirring at 500 rpm. The autoclave was then cooled to room temperature, weighed to make sure that no leakage had occurred during the reaction, and vented to release any unreacted 1,3-butadiene. The autoclave assembly was then reweighed to determine the amount of 1,3-butadiene consumed in the reaction. The reaction product was a clear, colorless, homogeneous liquid which contained 69.9% by weight monoether, 8.9% by weight diether, and 7.6% by weight octatriene, and 14.6% by weight 1,2-propanediol.

Example 2. Telomerization of 1.3-butadiene with σlycerol in the presence of 2-propanol. To a 400 ml glass autoclave equipped with a magnetic stir bar, there was added 0.0038 grams (0.0125 mmol) of palladium (II) acetylacetonate, 0.0066 grams (0.025 mmol) of triphenylphosphine, 28.78 grams (313 mmol) of glycerol, and 35 ml of 2-propanol. The autoclave was connected to a pressure gauge and the assembly was weighed. The autoclave assembly was evacuated and flushed three times with argon after which 37.8 grams (700 mmol) of 1,3-butadiene was added with a syringe. The autoclave was then reweighed, heated to 70°C and maintained at that temperature for 12 hours while stirring at 500 rpm. The autoclave was then cooled to room temperature, weighed to make sure that no

leakage had occurred during the reaction, and vented to release any unreacted 1,3-butadiene. The autoclave assembly was then reweighed to determine the amount of 1,3-butadiene consumed in the reaction. The reaction product was a clear, slightly colored liquid. The product contained 11.3 % by weight glycerol, 34.0 % by weight glycerol monoether, 21.7 % by weight glycerol diether, 2.1 % by weight glycerol triether, and 2.82% by weight octatriene.

Example 3. Telomerization of 1.3-butadiene with glycerol in the presence of 1.2-propanediol.

To a 400 ml glass autoclave equipped with a magnetic stir bar, there was added 0.0038 grams (0.0125 mmol) of palladium (II) acetylacetonate, 0.0066 grams (0.025 mmol) of triphenylphosphine, 10.31 grams (112 mmol) of glycerol, and 1.01 grams (13.3 mmol) of 1,2-propanediol. The autoclave was connected to a pressure gauge and the assembly was weighed. The autoclave assembly was evacuated and flushed three times with argon after which 13.5 grams (250 mmol) of 1,3-butadiene was added with a syringe. The autoclave was then reweighed, heated to 70°C and maintained at that temperature for 12 hours while stirring at 500 rpm. The autoclave was then cooled to room temperature, weighed to make sure that no leakage had occurred during the reaction, and vented to release any unreacted 1,3- butadiene. The autoclave assembly was then reweighed to determine the amount of 1,3-butadiene consumed in the reaction. The reaction product separated into a light yellow upper liquid phase and a clear, colorless lower liquid phase. The combined phases contained 1.3% by weight 1,2-propanediol, 5.1 % by weight 1,2-propanediol monoether, 0.8% by weight 1,2-propanediol diether, 6.9% by weight glycerol, 15.0 % by weight glycerol monoether, 43.0 % by weight glycerol diether, 17.8% by weight glycerol triether, and 10.0% by weight octatriene.

Example 4. Comparative Solvent Effects on the

Telomerization of 1.3-butadiene with glycerol

The procedure described in Example 1 was followed in producing the data listed in Table 1.

The data shows that isopropanol is the most effective solvent for improving the yield of telomerized product while keeping the amount of octatriene to a minimum. The reaction time is also considerably shorter in the presence of isopropanol.

TABLE l ^β

SOLVENT EFFECT ON TELOMERIZATION

OF BUTADIENE WITH GLYCEROL

%Telomers

Solvent %BD ^b %01io ^c Mono Tri Time(hr)

NONE 98 7.01 1.67 71.19 8.43 14 toluene 63 54.5 28.4 15.0 10 diethylether 8.0 52.8 18.2 11.5 3.0 10

THF 16 37.8 31.7 30.5 10 isopropanol 100 3.8 50.8 36.2 4.2 1.5 ethyl acetate 15 83.2 16.8 10 acetone 65 10.7 27.8 47.5 10.6 10 acetonitrile 98 12.5 26.6 47.3 10.0 10

DMSO 99 25.9 33.9 29.0 4.2 10 a- molar ratio Pd(acac) ₂ :PPh ₃ :butadiene:glycerol =

1:2:4100:2000 b- %BD is the % of butadiene consumed in the reaction. c- % oligomer is % octatriene

Example 5. Effect of Catalyst Concentration on Telomerization

The use of low concentrations of catalyst is exemplified in the data presented in Table 2. The results which were obtained in a study of the effect of catalyst concentration in the telomerization of 1,3-butadiene with glycerol are illustrative of the process of the present invention.

TABLE 2 ¹ EFFECT OF CATALYST CONCENTRATION IN THE TELOMERIZATION OF BUTADIENE WITH GLYCEROL

%Telomers

Pd: : BD ^a %BD ^C %01igomer ^b Mono Di Tri Timefhr)

1: 9184 100 4.8 54.5 32.9 2.2 2

1: 17908 100 5.8 49.5 38.1 3.0 5

1: 31848 96 5.9 49.6 34.9 2.5 7

1: 56880 100 7.6 48.9 33.8 2.5 10

1: 66064 94 8.8 54.2 31.6 1.9 20

1: 84432 78 10.6 60.9 23.6 1.4 25 a- BD is butadiene. b- % oligomer is % octatriene c- %BD is the % of butadiene consumed in the reaction. 1- temperature - 70°C; solvent - isopropanol

Example 6. Preparation of the octadienyl ethers of neopentylgl col (2.2-dimethyl-l,3-propanediol) .

To a 400 ml glass autoclave equipped with a magnetic stir bar, there was added 0.0038 grams (0.0125 mmol) of palladiu (II) acetylacetonate, 0.0066 grams (0.025 mmol) of triphenylphosphine, and 86.7 grams (832 mmol) of 2,2- dimethyl-1,3-propanediol. The autoclave was connected to a pressure gauge and the assembly was weighed. The autoclave assembly was evacuated and flushed three times with argon after which 67.5 grams (1250 mmol) of 1,3-butadiene was added with a syringe. The autoclave was then heated to 70°C and maintained at that temperature for 10 hours while stirring at 500 rpm. The autoclave was then cooled to room temperature, weighed to make sure that no leakage had occurred during the reaction, and vented to release any unreacted 1,3-butadiene. The autoclave assembly was then reweighed to determine the amount of 1,3-butadiene consumed in the reaction. The reaction product was a clear, colorless liquid which contained 88% by weight monoether, 7.6% by weight diether, and 4.4% by weight octatriene.

Example 7. Preparation of the octadienyl ethers of salicylaldehvde.

A 125 mL steel autoclave was charged with

salicylaldehyde (24.4 g, 0.200 mole) , Pd(acac) ₂ (12.2 mg, 40 μmol) and triphenyl-phosphine (15.7 mg, 60 μmol) . The air in the autoclave was replaced with N ₂ by means of three pump/purge cycles. The autoclave contents were cooled to 0°C and butadiene (24.8 g, 0.458 mole) was added with a syringe. The autoclave was sealed and the contents were allowed to warm to ambient temperature before being heated at 70°C for a period of 12 h. The maximum autogenous pressure that developed in the autoclave was 96 psi. The autoclave was then left to stand overnight at ambient temperature and the unreacted butadiene was vented. The amount of butadiene that reacted was calculated by difference to be 85%. GC analysis (non-quantitative) of the reaction mixture showed 7.4% unreacted salicylaldehyde, 83.6% of various O-octadienyl-salicylaldehyde ether telomers (three main components) and 6.0% of several side products. The crude product was dissolved in 100 mL of ether and washed with 5% aq. NaOH solution. The organic layer was washed with brine, dried over MgS0 ₄ , filtered and concentrated with a rotary evaporator to afford 40.4 g (88%) of salicylaldehyde telo er products free of unreacted salicylaldehyde.

Example 8. Preparation of the octadienyl ethers of Dehvdol LS 2 (Henkel KGaA. C _1: -C _K alcohols with mean ethoxylation *-=

To a 125 ml glass autoclave with a magnetic stir bar there was added Pd(acac) ₂ (0.0076 g, 0.025 mmol), PPh ₃ (0.0132 g, 0.050 mmol), and Dehydol LS 2 (35.1 g, 125 mmol) . The autoclave was connected to a pressure gauge apparatus and the whole assembly was weighed. The autoclave assembly was evacuated and flushed with argon three times. Butadiene (6.75 g, 125 mmol) was added to the autoclave and all valves and ports were closed. The assembly was reweighed to accurately determine the amount of butadiene added. The autoclave was heated to 70~c for 12 hours while

stirring at approximately 500 RPM. The system was allowed to cool to room temperature and then reweighed to verify that no loss of butadiene due to leakage had taken place. Any remaining butadiene was vented and the assembly was reweighed one last time to determine the amount of butadiene reacted. Complete butadiene conversion was observed and the product solution was clear, nearly colorless, and homogeneous. Analysis by GC/MS confirmed the presence of octatrienes, C ₁₂ OH, C ₁₂ OH with 1 to 2 EO units, octadienyl ethers of C ₁₂ OH with 0 to 4 EO units, C ₁₄ 0H, C ₁₄ OH with 1 to 2 EO units, and octadienyl ethers of C140H with 0 to 2 EO units.

Example 9. Preparation of the octadienyl ethers of Tergitol NP 4 (Ashland Chemical, Nonylphenol with mean ethoxylation = 4)

To a 125 ml glass autoclave with a magnetic stir bar there was added Pd(acac) ₂ (0.0076 g, 0.025 mmol), PPh ₃ (0.0132 g, 0.050 mmol), and Tergitol NP 4 (9.9 g, 25 mmol). The autoclave was connected to a pressure gauge apparatus and the whole assembly was weighed. The autoclave assembly was evacuated and flushed with argon three times. Butadiene (6.75 g, 125 mmol) was added to the autoclave and all valves and ports were closed. The assembly was reweighed to accurately determine the amount of butadiene added. The autoclave was heated to 70oc for 12 hours while stirring at approximately 500 RPM. The system was cooled to room temperature and then reweighed to verify no loss by leakage. Any remaining butadiene was vented and the assembly reweighed one last time to determine the amount of butadiene reacted. Near complete (>95%) butadiene conversion was observed. The product solution was green colored and homogeneous. Analysis by GC/MS (direct probe NH ₃ C.I.) confirmed the presence of octatrienes, nonylphenol with 3 to 8 EO units and octadienyl ethers of nonylphenol with 3 to 6 EO units.

Example 10. Preparation of Octadienyl Ethers of Glucose

A one gallon autoclave was charged with Pd(acac) ₂ (0.8685 g, 2.85 mmol), triphenylphosphine (1.495 g, 5.700 mmol), anhydrous glucose (513 g, 2.85 mol), isopropyl alcohol (820 g, 13.64 mol) and de-ionized water (110 g, 6.11 mol). The air in the autoclave was replaced with nitrogen by three pump/purge cycles (evacuation to -0.2 torr and bleeding N ₂ back in to ambient pressure) while the reactants were mixed by stirring at 600 RPM after which the butadiene (1385 g, 25.65 mol) was added. The contents were heated to 65°C for 10 hrs after which they were allowed to cool to room temperature and the unreacted butadiene (<15% of charge) was vented. A light yellow/green clear solution was obtained after filtration to remove residual solid glucose (<5% of charge) . The crude solution had the following composition (weight%) : glucose octadienyl ethers (54) , side products (11, mainly isopropyloctadienyl ether, octatrienes and octadienol) ; solvent (35) . Removal of the solvent and side products gave approximately 1.45 kg glucose octadienyl ether mixture with the following characteristics: Iodine value 280; hydroxyl value 250; average degree of substitution 2.5 (as determined by H ¹ NMR), glucose <1% by weight. GLC analysis revealed the following product distribution (area %) : monoether (6) , diether (42) ; triether (52) ; tetraether (trace) ; pentaether (not detectable by GLC) . GLC results based on trimethylsilane derivatized products under the following conditions: Supelco SPB-5 column, temperature program from 200 to 320°C at 10°/min.

Example 11. Preparation of Octadienyl Ether of Methyl 4- hvdroxybenzoate

A 75 ml capacity, two-port steel autoclave, containing a magnetic stirring bar and fitted with a pressure gauge, was charged with Pd(acac) ₂ (3.1 mg, 0.010 mmol), triphenylphosphine (5.3 mg, 0.020 mmol), methyl 4-

hydroxybenzoate (1.52g, 10 mmol), and isopropyl alcohol (2.0 ml) . The air in the autoclave was replaced with nitro¬ gen by three pump/purge cycles (evacuation to -0.2 torr and bleeding N ₂ back in to ambient pressure) while the reactants were mixed by stirring. The apparatus was cooled to -70°C and butadiene (-2 ml, 25 mmol) was introduced into the autoclave while N ₂ was swept over the top of the reactants and out of the opening. The autoclave was sealed and the mixture was allowed to warm to ambient temperature before being placed in an oil bath heated to 50°C. The reaction mixture was stirred at this temperature for a period of 12 h. The unreacted butadiene was vented and GC analysis (non- quantitative) of the crude product showed a product distribution of 19.8% branched phenol ether, 53.4% linear phenol ether, 23.0% octatrienes, and 2.5% isopropyl alcohol telomer.

Example 12. Preparation of Octadienyl Ether of Pentaervthritol A 125 ml capacity two port steel autoclave, containing a stirring bar and fitted with a pressure gauge, was charged with Pd(acac) ₂ (7.6 mg, 0.025 mmol), triphenylphosphine (13.2 mg, 0.05 mmol), pentaerythritol (17.lg, 125 mmol), and isopropyl alcohol (20 ml). The air in the autoclave was replaced with argon by three pump/purge cycles (evacuation to about 0.2 torr and bleeding Ar back in to ambient pressure) while the reactants were mixed by stirring. The apparatus was cooled to -70°C and butadiene (about 20 ml, 13.7g, 254 mmol) was introduced with a syringe into the autoclave while Ar was swept over the top of the reactants and out of the opening. The autoclave was sealed and the mixture was allowed to warm to ambient temperature before being placed in an oil bath heated to 50°C. The mixture was stirred at this temperature for a period of 14.5 h. The reactor was vented to release any unreacted amount of butadiene. The autoclave

assembly was reweighed, and it was determined that 100% of the butadiene was consumed by the reaction. GLC of the crude reaction mixture showed a product distribution of 3.4 area % pentaerythritol mono-octadienyl ether, 36.3 area % diether, 53.1 area % triether, 3.6 area % tetraether, octatriene and isopropyl alcohol telomers reported together as 4.0 weight % (ratio about 1:1); only 0.6 area % pentaerythritol was present.

Example 13. Telomerization of Butadiene with 4- Hydroxybenzoic Acid

A 100 mL capacity, two-port glass autoclave, containing a magnetic stirring bar and fitted with a pressure gauge and cap, was charged with Pd(acac) ₂ (3.0 mg, 9.8 /mol) , tris(o-tolyl)phosphite (7.0 mg, 19.9 mol) , 4- hydroxybenzoic acid (1.38 g, 10 mmol) and isopropyl alcohol solvent (2 mL) . The apparatus was cooled below ambient temperature and the air in the autoclave was replaced with nitrogen by means of three pump/purge cycles (evacuation of the reactor to approximately 0.2 torr and refilling with nitrogen to ambient pressure) while the reactants were stirred. Liquid butadiene (2.4 g, approximately 3 mL, 40 mmol) was introduced into the autoclave by syringe while the reactants were blanketed with nitrogen. The autoclave was sealed and the mixture was allowed to warm to room temperature. The apparatus was placed in an oil bath heated to 70°C and allowed to react with stirring for a period of 12 h. The unreacted butadiene was vented. The conversion of butadiene was 50% based on the weight of the reactants before and after venting. Qualitative GC and GC/MS analysis of the reaction mixture revealed that the main products were octadienyl esters.

Example 14. Telomerization of Butadiene with Glycoliσ Acid A 100 mL capacity, two-port glass autoclave, containing a magnetic stirring bar and fitted with a

pressure gauge and cap, was charged with Pd(acac) ₂ (7.6 mg, 25 μmol) , triphenylphosphine (17.6 mg, 50 μmol) , glycolic acid (1.90 g, 25 mmol), and isopropyl alcohol (5.0 mL) . The apparatus was cooled below ambient temperature and the air in the autoclave was replaced with nitrogen by means of three pump/purge cycles (evacuation of the reactor to approximately 0.2 torr and refilling with nitrogen to ambient pressure) while the reactants were stirred. Liquid butadiene (4.7 g, approximately 5 mL, 73 mmol) was introduced into the autoclave by syringe while the reactants were blanketed with nitrogen. The autoclave was sealed and the mixture was allowed to warm to room temperature. The apparatus was placed in an oil bath heated to 70°C and allowed to react for a period of 12 h. The unreacted butadiene was vented. The conversion of butadiene was 34% based on the weight of the reactants before and after venting. Qualitative GC (area %) analysis of the products indicated the following distribution: unreacted acid, 54%; butenyl esters, 14%; octadienyl esters, 10%; isopropanol telomers, 10%. Product identities were confirmed by GC/MS analysis.

Example 15. Telomerization of Butadiene with Dimethylolpropionic Acid A 100 mL capacity, two-port glass autoclave, containing a magnetic stirring bar and fitted with a pressure gauge and cap, was charged with Pd(aσac) ₂ (15.2 mg, 50 μmol), triphenylphosphine (26.2 mg, 0.10 mmol), dimethylolpropionic acid (DMPA) (3.35 g, 25 mmol), and dimethylacetamide solvent (10.0 L) . The air in the autoclave was replaced with nitrogen by means of two pump/purge cycles (evacuation of the reactor to approximately 0.2 torr and refilling with nitrogen to ambient pressure) while the reactants were mixed by stirring. The apparatus was cooled to -70° and butadiene (approx. 10 mL, 125 mmol) was introduced into the autoclave

while the reactants were blanketed with nitrogen. The autoclave was sealed and the mixture was allowed to warm to room temperature before being placed in an oil bath heated to 70°C. The reaction mixture was stirred at this temperature for 15 hours. The unreacted butadiene was vented. Butadiene conversion was found by difference to be 64%. Qualitative GC (area %) analysis revealed the following distribution: unreacted DMPA, <1%; monoether telomers, 88%; diether telomers, 3%; octatrienes and other side products, <10%. The ether telomers were identified by GC/MS and GC/IR analysis.

Example 16. Telomerization of Butadiene with Octadec-9- vnoic Acid A 125 mL capacity two port steel autoclave containing a magnetic stirring bar and fitted with a pressure gauge, rupture disk and inlet valve was charged with Pd(acac) ₂ (0.5 mg, 1.6 μmol), tris(o-tolyl)phosphite (1.2 mg, 3.2 μmol), octadec-9-ynoic acid (1.40 g, 5.0 mmol) and 2-propanol (2.0 mL) . The apparatus was cooled to -50°C with a dry ice/acetone bath and the air inside the autoclave was replaced with nitrogen by means of three evacuate/fill cycles (the reactor was evacuated to 0.2 torr and filled with nitrogen to ambient pressure) while the contents were mixed by stirring. Butadiene (approx. 1 mL, 1.5 g, 28 mmol) was introduced into the autoclave through the uncapped side port with a syringe while nitrogen was swept over the reaction components. The autoclave was sealed and the apparatus was allowed to warm to near ambient temperature before being placed in an oil bath heated to 50°C. The reaction mixture as stirred at this temperature for a period of 12 h. The maximum autogenous pressure that developed in the reactor was 6.0 bar. Unreacted butadiene was vented and GC analysis of the resulting mixture showed quantitative conversion of the acid to octadienyl esters.

Example 17. Preparation of Octadienyl Ethers of Methylglucoside

A one gallon autoclave was charged with Pd(acac) ₂ 0.675 g, 2.22 mmol), triphenylphosphine (1.25 g, 4.76 mmol), methylglucoside (525 g, 2.71 mol), isopropyl alcohol (820 g, 13.64 mol) and de-ionized water (75 g, 4.17 mol). The air in the autoclave was replaced with nitrogen by three pump/purge cycles (evacuation to -0.2 torr and bleeding N ₂ back in to ambient pressure) while the reactants were mixed by stirring at 600 RPM after which the butadiene (1250 g, 23.15 mol) was added. The contents were heated to 70°C for 10 hrs after which they were allowed to cool to room temperature and the unreacted butadiene (<15% of charge) was vented. A light yellow/green clear solution was obtained after filtration to remove residual solid methylglucoside (<5% of charge) . Removal of the solvent and side products (mainly isopropyloctadienyl ether, octatrienes, and octadienol) yielded approximately 1.3 kg methylglucoside octadienyl ether mixture with the following characteristics: iodine value 258; hydroxyl value 191; average degree of substitution 2.2 (as determined by H ¹ NMR, methylglucoside <1% by weight. GLC analysis revealed the following product distribution (area %) : monoether (7) , diether (52) ; triether (39) ; tetraether (2) . GLC results based on trimethylsilane derivatized products under the following conditions: Supelco SPB-5 column, temperature program from 200 to 320°C at 10°/min.

Example 18. Preparation of Octadienyl Ethers of Butylglucoside

A 125 ml capacity, two-port steel autoclave, containing a magnetic stirring bar and fitted with a pressure gauge, was charged with Pd(acac) ₂ (12.7 mg, 0.0417 mmol), triphenylphosphine (23.6 mg, 0.090 mmol), butylglucoside (11.0 g, 46.6, mmol), and isopropyl alcohol (20 ml) . The air in the autoclave was replaced with argon

by three pump/purge cycles (evacuation to -0.5 torr and bleeding argon back in to ambient pressure) while the reactants were mixed by stirring. The apparatus was cooled to approximately -50°C and butadiene (21.0 g, 388 mmol) was introduced into the autoclave while argon was swept over the top of the reactants and out of the opening. The autoclave was sealed and the mixture was allowed to warm to ambient temperature before being placed in an oil bath heated to 70°C. The reaction mixture was stirred at this temperature for a period of 12 h. The unreacted butadiene was vented (1 g) and the remaining clear solution was distilled to remove the solvent and octatriene side products, to yield 20.8 g of a clear liquid product with the following analytical data: average degree of substitution by ¹ H-NMR = 2.1; distribution by GLC (area %) : butylglucoside (<1%) , butylglucoside monooctadienylethers (17%), butylglucoside dioctadienylethers (61%), butylglucoside trioctadienylethers (18%) , butylglucoside tetraoctadienylethers (<2%) . GLC results based on trimethylsilane derivatized products under the following conditions: Supelco SPB-5 column, temperature program from 200 to 320°C at 10°C/min.

Example 19. Preparation of Octadienyl Ethers of Sucrose A one gallon autoclave was charged with Pd(acac) ₂ 0.7550 g, 2.48 mmol), triphenylphosphine (1.302 g, 4.96 mmol), sucrose (510 g, 1.49 mol), isopropyl alcohol (820 g, 13.64 mol) and de-ionized water (llOg, 6.11 mol). The air in the autoclave was replaced with nitrogen by three pump/purge cycles (evacuation to -0.2 torr and bleeding N ₂ back in to ambient pressure) while the reactants were mixed by stirring at 600 RPM after which the butadiene (1340 g, 24.81 mol) was added. The contents were heated to 65°C for 10 hrs after which they were allowed to cool to room temperature and the unreacted butadiene (<15% of charge) was vented. A light yellow/green clear solution was

obtained after filtration to remove residual solid sucrose (<5% of charge) . Removal of the solvent and side products (mainly isopropyloctadienyl ether, octatrienes, and octadienol) yields approximately 1.44 kg sucrose octadienyl ether mixture with the following characteristics: iodine value 282; hydroxyl value 160; average degree of substitution 5.5 (as determined by H ¹ NMR, sucrose <1% by weight.

Example 20. Deodorized Glucose Octadienyl Ethers

A two kg sample of a glucose telomer, obtained as described in example 18, was passed through a wiped film evaporator with an area of 0.1 m ² at a feed rate of 0.6 liter/hour, a temperature of 60°C and a vacuum of 3 mm Hg. The wiper velocity was adjusted to 200 RPM (forward) . Steam was fed to the system at an amount of ca. 0.2 g/1 g of the glucose telomer and condensed in a dry ice cooler together with volatiles. After 3.5 h, 1.87 kg of deodorized glucose telomers was obtained. 0.13 kg of volatiles with bad odor was separated from the condensed water, consisting mainly of isopropyloctadienylether and octadienol, according to supercritical fluid chromatography (SFC) analysis.

Comparative Example. Solvent Effect on the Telomerization of 1.3-butadiene with 1.4-butanediol.

The procedure of example 2 was followed using the quantities of 1,4-butanediol, isopropyl alcohol (IPA) , and 1,3-butadiene indicated in Table 3A. The results which are listed in Table 3B show that the presence of isopropanol in the reaction increases the product yield and the consumption of butadiene. The data in Table 3 also show that efforts to repeat the results disclosed in British Patent No. 2,114,974 (experiments D and E) were not successful, and that the use of isopropyl alcohol as solvent gave markedly enhanced conversions of butadiene and

1,4-butanediol to telomer product.

TABLE 3A TELOMERIZATION OF 1,4-BUTANEDIOL RAW MATERIALS USED

Exp. BD ^a Diol* IPA Pd: BD ^a : diol ^a Time

No. ( rams) (grams) (grams) molar ratio hrs)

A 18.2 74.1 15.7 1: 26960: 65840 12

B 13.2 52.1 15.7 l: 19520: 46240 13

C 13.5 33.9 19.6 l: 20000: 30080 6

D 13.7 45.5 0 1: 24190: 48095 4

E 13.6 45.3 0 l: 24000: 47904 4

TABLE 3B

TELOMERIZATION OF 1,4-BUTANEDIOL

PRODUCT ANALYSES

Exp. Remaining ⁰ %Te omers

No. %BD ^d diol % %01ig ^b Mono Di Ref

A 36 58.6 2.2 36.7 2.5 1

B 83 59.5 2.4 37.0 1.1 1

C 100 51.7 4.3 41.0 1.9 1

D 17 98.1 ND 1.9 ND 2

E 17 98.4 ND 1.6 ND 2 a- BD is butadiene, diol is 1,4-butanediol. b- % oligomer is % octatriene c- % diol is the percent of the original diol which has not reacted, and remains in the solution. d- %BD is the % of butadiene consumed in the reaction.

1- catalyst- Pd(acac) ₂ : 2 (Ph),P; reaction temperature = 70OC.

2- catalyst- Pd(OAc) ₂ (Ph ₃ P) ₂ ; 1.7 equiv. Ni(OAc) ₂ 4H ₂ 0 added; temperature = 75©C as disclosed in British Patent No.

2,114,974.