WO2012103156A1 - Surfactants - Google Patents

Abstract

This application relates to derivatives of hydrocarbon terpenes (e.g., myrcene or farnesene), to methods of making the derivatives, and to the use of the derivatives as surfactants.

Description

SURFACTANTS

CROSS REFERENCE TO RELATED APPLICATIONS

[001] This application claims the benefit of U.S. Provisional Patent Application No.

61/436,165, filed January 25, 201 1 , U.S. Provisional Patent Application No. 61/486, 156 filed May 13, 201 1 , U.S. Provisional Patent Application No. 61/527,041 , filed August 24, 201 1 , U.S. Provisional Patent Application No. 61/543,747, filed October 5, 201 1 , and U.S. Provisional Patent Application No. 61/544,257, filed October 6, 201 1 , each of which is incorporated herein by reference in its entirety as if put forth fully below.

FIELD

[002] This application relates to derivatives of hydrocarbon terpenes comprising at least one conjugated diene (e.g., myrcene or farnesene), methods of making the derivatives, and the use of the derivatives as surfactants. The surfactants have a wide variety of industrial and domestic applications.

BACKGROUND

[003] Conjugated terpenes such as myrcene and the sesquiterpene β-farnesene can be synthesized via biological routes. For example, myrcene and β-farnesene can be produced in high yield from modified yeast, as described in U.S. Patent Nos. 7,399,323 and 7,659,097, each of which is incorporated herein by reference in its entirety, as if put forth fully below.

[004] Most currently available surfactants are derived from petrochemicals. In some cases, surfactants are derived from oleochemicals such as vegetable oils.

[005] A need exists for new surfactants derived from renewable carbon sources other than conventional oleochemicals, such as from sugars or biomass.

SUMMARY

[006] Described herein are surfactants that comprise or are derived from Diels-Alder adducts between a hydrocarbon terpene comprising a conjugated diene (e.g., myrcene, β- farnesene, or a-farnesene) and a dienophile, methods of making the surfactants, and to the use of the surfactants in industrial and domestic applications. For example, certain variations of the surfactants described herein have utility in forming emulsions (e.g., for personal care products, cleaning products, or agricultural products) or as detergents (e.g., laundry detergents). [007] The surfactants comprise a ring structure resulting from a Diels- Alder reaction between a hydrocarbon terpene comprising a conjugated diene and a dienophile, with one or more hydrophobic tails originating from the hydrocarbon terpene attached to the ring structure, and one or more hydrophilic heads originating from or derived from the dienophile attached to the ring structure. The hydrocarbon terpene and the dienophile may each be selected to impart desired properties to the surfactant. A Diels- Alder adduct may undergo chemical derivatization following the Diels-Alder reaction to form a surfactant having desirable properties. The Diels- Alder adducts described herein may be designed for use as nonionic surfactants, cationic surfactants, anionic surfactants, or zwitterionic surfactants (e.g., amine oxide).

[008] Through selection of the hydrocarbon terpene and the dienophile, it is possible to build Diels-Alder adducts that have varying configurations of hydrophobic tails and hydrophilic heads attached to the ring structure that results from the Diels-Alder reaction (e.g., a

cyclohexenyl or a cyclohexyl ring). For example, in certain variations, the surfactants described herein comprise one hydrophobic tail originating from a hydrocarbon terpene and one hydrophilic head originating from or derived from a dienophile attached to the ring structure. In some variations, the surfactants comprise one hydrophobic tail originating from a hydrocarbon terpene and two hydrophilic heads originating from or derived from one or more dienophiles attached the ring structure. In some variations, the surfactants comprise two hydrophobic tails originating from a hydrocarbon terpene and one hydrophilic head originating from or derived from a dienophile attached to the ring structure. In certain variations, the surfactants described herein comprise two hydrophobic tails originating from a hydrocarbon terpene and two hydrophilic heads originating from one or more dienophiles attached to the ring structure.

[009] Any suitable hydrocarbon terpene having a conjugated diene may be used to make the surfactants described herein. In some cases, the carbon number of the hydrocarbon terpene may be varied to modulate the hydrophobicity of the surfactant. The conjugated diene may be located at a terminal position of the hydrocarbon terpene in some variations, and in other variations, the conjugated diene is located at an internal position of the hydrocarbon terpene. In some variations, the hydrocarbon terpene is myrcene, β-farnesene, a-farnesene, or β-springene. In some variations, the hydrocarbon terpene is β-farnesene, which may in certain instances be derived from a sugar using a genetically modified organism.

[010] Any suitable dienophile may be used to make the surfactants described herein.

The dienophile may be selected to impart desired hydrophilic properties, or to contain certain functional groups that can be derivatized to impart desired hydrophilic properties to a Diels- Alder adduct. Non-limiting examples of suitable dienophiles include maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, dialkyl maleates, dialkyl fumarates, dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates, (dialkylamino)alkyl acrylates, dialkyl acetylene

dicarboxylates, vinyl ketones, maleimide and substituted maleimides, dialkyl azidocarboxylates, acetylene dicarboxylic acid, dialkyl acetylene dicarboxylates, vinyl sulfonates, vinyl sulfmates, vinyl sulfoxides, and combinations thereof.

[Oil] In some variations, the Diels-Alder adduct is a neutral compound that functions as a nonionic surfactant. For example, the Diels-Alder adduct may be an alcohol (e.g., a primary alcohol), or a polyol (e.g., a diol). In some variations, a nonionic surfactant is an alkoxylated alcohol. For example, a surfactant may comprise one or more polyethoxylate chains having the formula ^"CH2 ⁿ , where n represents an average number of ethoxylate units and is in a range from about 1 to about 200. In certain variations, n is in a range from about 5 to about 20, e.g., n is about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In some variations, a nonionic surfactant comprises two polyethoxylate chains each having the formula

ere n is as described above. In certain embodiments, the terminal hydrogen can be replaced with a terminal group known to those of skill in the art such as a methyl group.

[012] In some variations, a nonionic surfactant comprises at least one glucoside group.

In some variations, a nonionic surfactant comprises at least one glucamide group. In some variations, a nonionic surfactant comprises at least one amine group. In some variations, a nonionic surfactant comprises at least one alkanolamide group.

[013] In some variations, the Diels-Alder adduct is adapted for use as an anionic surfactant. For example, a Diels-Alder adduct may comprise a carboxylate salt, a sulfonate salt, a sulfate salt, or a phosphate salt.

[014] In some variations, the Diels-Alder adduct is adapted for use as a cationic surfactant. For example, a Diels-Alder adduct may comprise a quaternary ammonium ion. [015] In some variations, the Diels-Alder adduct is adapted for use as a zwitterionic surfactant. For example, a Diels-Alder adduct may comprise an amine-oxide group, or may be a betaine.

[016] The surfactants described herein may be used in a variety of formulations employing surfactants, e.g., emulsions, detergents, industrial and domestic cleaning products, personal care products, and agricultural products. For example, certain nonionic surfactants described herein form stable emulsions with oils that are useful in personal care products, agriculture, and cleaning applications are described herein. Detergent formulations (e.g., laundry detergents) may comprise one or more surfactants (e.g., nonionic surfactants) described herein. Surfactants described herein may be utilized in laundry aids, such as fabric softeners, bleaches, stain treatments, and the like.

[017] Also described herein are methods for making surfactants. The methods comprise reacting a hydrocarbon terpene comprising a conjugated diene with a dienophile under conditions sufficient to form a Diels-Alder adduct having a ring structure, wherein the Diels- Alder adduct comprises a hydrophobic tail and a hydrophilic head attached to the ring structure. In certain variations, the methods comprise hydrogenating unsaturated carbon-carbon bonds on the Diels-Alder adduct. In some variations, the methods comprise derivatizing the Diels-Alder adduct to impart desired functional groups or to modify the hydrophilicity or solubility of the adduct.

[018] In some variations, the methods comprise derivatizing the Diels-Alder adduct to form a nonionic surfactant, e.g., to form an alcohol or polyol (e.g., diol), a carboxylic acid or diacid, an alkoxylated alcohol or polyol (e.g., diol), an amine, an organic peracid, a glucoside, a glucamide, a carboxylic acid ester, an amide, or an alkanolamide. In some variations, the methods comprise derivatizing the Diels-Alder adduct to form an anionic surfactant, e.g., to form a carboxylate salt, a sulfonate salt, a sulfate salt, or a phosphate salt. In some variations, the methods comprise derivatizing the Diels-Alder adduct to form a cationic surfactant, e.g., to form a quarternary ammonium ion. In some variations, the methods comprise derivatizing the Diels-Alder adduct to form a zwitterionic surfactant, e.g., to form an amine oxide or a betaine.

BRIEF DESCRIPTION OF DRAWINGS

[019] FIGURE 1 shows 1H NMR spectrum of (E)-dimethyl 4-(4,8-dimethylnona-3,7- dienyl)cyclohex-4-ene-l,2-dicarboxylate of Example 5. [020] FIGURE 2 shows 1H NMR spectrum of dimethyl 4-(4,8- dimethylnonyl)cyclohexane-l,2-dicarboxylate of Example 6.

[021] FIGURE 3 shows 1H NMR spectrum of (4-(4,8-dimethylnonyl)cyclohexane- 1 ,2- diyl)dimethanol of Example 7.

[022] FIGURE 4A and FIGURE 4B show ¹³C NMR spectra of (4-(4,8- dimethylnonyl)cyclohane-l,2-diyl)dimethanol of Example 7.

[023] FIGURE 5 shows 1H NMR spectrum of a mixture of (E)-3-(4,8-dimethylnona-

3,7-dienyl)cyclohex-3-enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7-dienyl)cyclohex-3- enecarbaldehyde of Example 8.

[024] FIGURE 6A and 6B show GC/MS spectra of a mixture of (E)-3-(4,8- dimethylnona-3,7-dienyl)cyclohex-3-enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7- dienyl)cyclohex-3-enecarbaldehyde of Example 8.

[025] FIGURE 7 shows 1H NMR spectrum of a mixture of (3-(4,8- dimethylnonyl)cyclohexyl)methanol and (4-(4,8-dimethylnonyl)cyclohexyl)methanol of Example 9.

[026] FIGURES 8A-8C show 1H NMR spectra of a mixture of 1 -(4,8-dimethyl-nonyl)- cyclohexane-3-pentaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-pentaethylene glycol of Example 10.

[027] FIGURES 8D-8F show ¹³C NMR spectra of a mixture of 1 -(4,8-dimethyl-nonyl)- cyclohexane-3-pentaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-pentaethylene glycol of Example 10.

[028] FIGURES 9A-9C show 1H NMR spectra of a mixture of 1 -(4,8-dimethyl-nonyl)- cyclohexane-3-decaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-decaethylene glycol of Example 11.

[029] FIGURES 9D-9F show ¹³C NMR spectra of a mixture of 1 -(4,8-dimethyl-nonyl)- cyclohexane-3-decaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-decaethylene glycol of Example 11.

[030] FIGURES 1 OA- IOC show 1H NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3-pentadecaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4- pentadecaethylene glycol of Example 12.

[031] FIGURES 10D-10F show ¹³C NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3-pentadecaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4- pentadecaethylene glycol of Example 12. [032] FIGURES 1 lA-1 1C show 1H NMR spectra of l-(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-pentaethylene glycol) of Example 13.

[033] FIGURES 1 lD-1 IF show ¹³C NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3,4-bis(methyl-pentaethylene glycol) of Example 13.

[034] FIGURES 12A-12C show 1H NMR spectra of l-(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-decaethylene glycol) of Example 14.

[035] FIGURES 12D-12F show ¹³C NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3,4-bis(methyl-decaethylene glycol) of Example 14.

[036] FIGURES 13A-13C show 1H NMR spectra of l-(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-decapentaethylene glycol) of Example 15.

[037] FIGURES 13D-13F show ¹³C NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3,4-bis(methyl-decapentaethylene glycol) of Example 15.

[038] FIGURE 14A shows a plot of surface tension (mN/m) vs. logio(surfactant concentration in ppm) for the surfactant of Example 12.

[039] FIGURE 14B shows a plot of surface tension (mN/m) vs. logio(surfactant concentration in ppm) for the surfactant of Example 13.

[040] FIGURE 14C shows a plot of surface tension (mN/m) vs. logio(surfactant concentration in ppm) for the surfactant of Example 14.

[041] FIGURE 14D shows a plot of surface tension (mN/m) vs. logio(surfactant concentration in ppm) for the surfactant of Example 15.

DETAILED DESCRIPTION

[042] Described herein are surfactants that comprise or are derived from Diels-Alder adducts between a hydrocarbon terpene comprising a conjugated diene moiety (e.g., myrcene, β- farnesene, or a-farnesene) and a dienophile, methods of making the surfactants, and to the use of the surfactants in industrial and domestic applications. For example, certain variations of the surfactants described herein have utility in forming emulsions (e.g., for use in personal care products, cleaning products, agricultural products, and the like), as cleaning products (e.g., for use in personal care products, detergents such as laundry detergents, hard surface cleaners, industrial cleaners and the like), as laundry aids (e.g., for use in laundry detergents, fabric softeners and the like). Certain surfactants derived from Diels-Alder reaction between a hydrocarbon terpene comprising a conjugated diene and a dieneophile are disclosed in U.S. Provisional Patent Application Serial No. 61/436,165, filed January 25, 201 1 , and U.S. Provisional Patent Application Serial No. 61/527,041, filed August 24, 2011, each of which is incorporated herein by reference in its entirety as if put forth fully below.

[043] The surfactants comprise a ring structure resulting from a Diels-Alder reaction between a hydrocarbon terpene comprising a conjugated diene and a dienophile, with one or more hydrophobic tails originating from the hydrocarbon terpene attached to the ring structure, and one or more hydrophilic heads originating from the dienophile attached to the ring structure. The hydrocarbon terpene and the dienophile may be selected to impart desired properties to the surfactant. A Diels-Alder adduct may undergo chemical derivatization following the Diels- Alder reaction to form a surfactant having desirable properties. The Diels-Alder adducts described herein may be designed for use as nonionic surfactants, cationic surfactants, anionic surfactants, or zwitterionic surfactants (e.g., amine oxide).

[044] Provided below is Section A), which includes some definitions. Section B) below describes sources of hydrocarbon terpenes comprising a conjugated diene. Section C) includes non- limiting examples of formation of Diels-Alder adducts from which the surfactants can be derived. Section D) below provides non-limiting examples of dienophiles that can be used in the Diels-Alder reaction to make the surfactants. Section E) below provides non- limiting examples of hydrocarbon terpenes comprising a conjugated diene that can be used in the Diels-Alder reaction to make the surfactant. Section F) below provides non-limiting examples of Diels-Alder adducts that can be formed. Section G) below provides non-limiting examples of chemical modifications that can be performed on a Diels-Alder adduct to make a surfactant having desired properties. Section H) below provides non-limiting examples of farnesene-based Diels-Alder adducts from which surfactants can be derived. Section J) below provides non-limiting examples of variations of surfactants that can be derived from the Diels- Alder adducts (nonionic, anionic, cationic, zwitterionic). Section K) below provides non- limiting examples of applications for the surfactants described herein. It should be understood that Sections A)-K) are provided for organization purposes only. Any suitable dienophile from Section D) may be reacted with any suitable hydrocarbon terpene from Section E).

A) Definitions

[045] In the following description, all numbers disclosed herein are approximate values, regardless whether the word "about" or "approximate" is used in connection therewith.

Numbers may vary by 1 percent, 2 percent, 5 percent, or, sometimes, 10 to 20 percent.

Whenever a numerical range with a lower limit, R^L, and an upper limit, R^u, is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R=R^L+k*(R^u-R^L), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent or 100 percent. Moreover, any numerical range defined by two R numbers as defined in the above is also specifically disclosed.

[046] "Terpene" as used herein is a compound that is capable of being derived from isopentyl pyrophosphate (IPP) or dimethylallyl pyrophosphate (DMAPP), and the term terpene encompasses hemiterpenes, monoterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, tetraterpenes and polyterpenes. A hydrocarbon terpene contains only hydrogen and carbon atoms and no heteroatoms such as oxygen, and in some embodiments has the general formula (C₅H₈)_n, where n is 1 or greater. A "conjugated terpene" or "conjugated hydrocarbon terpene" as used herein refers to a hydrocarbon terpene comprising at least one conjugated diene moiety. It should be noted that the conjugated diene moiety of a conjugated terpene may have any stereochemistry {e.g., cis or trans) and may be part of a longer conjugated segment of a terpene, e.g., the conjugated diene moiety may be part of a conjugated triene moiety, but is not part of an aromatic ring. A conjugated hydrocarbon terpene may contain a conjugated diene at a terminal position {e.g., myrcene, farnesene) or the conjugated diene may be at an internal position {e.g., isodehydrosqualene or isosqualane precursor I or II). It should be understood that hydrocarbon terpenes as used herein also encompasses monoterpenoids, sesquiterpenoids, diterpenoids, triterpenoids, tetraterpenoids and polyterpenoids that exhibit the same carbon skeleton as the corresponding terpene but have either fewer or additional hydrogen atoms than the corresponding terpene, e.g., terpenoids having 2 fewer, 4 fewer, or 6 fewer hydrogen atoms than the corresponding terpene, or terpenoids having 2 additional, 4 additional or 6 additional hydrogen atoms than the corresponding terpene. Some non-limiting examples of conjugated hydrocarbon terpenes include isoprene, myrcene, a-ocimene, β-ocimene, a-farnesene, β- farnesene, β-springene, geranylfarnesene, neophytadiene, cw-phyta- 1,3 -diene, trans -phyta-1, 3- diene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II.

[047] Terpenes or isoprenoid compounds are a large and varied class of organic molecules that can be produced by a wide variety of plants and some insects. Some terpenes or isoprenoid compounds can also be made from organic compounds such as sugars by

microorganisms, including bioengineered microorganisms. Because terpenes or isoprenoid compounds can be obtained from various renewable sources, they are useful for making eco- friendly and renewable surfactants. In certain embodiments, the conjugated hydrocarbon terpenes as described herein are derived from microorganisms using a renewable carbon source such as a sugar that can be replenished in a matter of months or a few years unlike fossil fuels.

[048] "Isoprene" refers to a compound having the following structure:

or a stereoisomer thereof. [049] "Myrcene" refers to a compound having the following structure:

or a stereoisomer thereof. [050] "Ocimene" refers to a-ocimene, β-ocimene or a mixture thereof.

[051] "a-ocimene" refers to a compound having the following formula:

or a stereoisomer (e.g., s-cis isomer) thereof.

[052] "β-ocimene" refers to a compound having the following formula:

or a stereoisomer (e.g., s-cis isomer) thereof.

[053] "Farnesene" as used herein refers to a-farnesene, β-farnesene or a mixture thereof.

[054] "a-Farnesene" refers to a compound having the following structure:

or a stereoisomer (e.g., s-cis isomer) thereof. In some embodiments, a-farnesene comprises a substantially pure stereoisomer of a-farnesene. In some embodiments, a-farnesene comprises a mixture of stereoisomers, such as s-cis and s-trans isomers. In some embodiments, the amount of each of the stereoisomers in an α-farnesene mixture is independently from about 0.1 wt.% to about 99.9 wt.%, from about 0.5 wt.% to about 99.5 wt.%, from about 1 wt.% to about 99 wt.%, from about 5 wt.% to about 95 wt.%, from about 10 wt.% to about 90 wt.% or from about 20 wt.%) to about 80 wt.%, based on the total weight of the a-farnesene mixture of stereoisomers.

[055] "β-farnesene" refers to a compound having the following structure:

or a stereoisomer thereof. In some embodiments, β-farnesene comprises a substantially pure stereoisomer of β-farnesene. Substantially pure β-farnesene refers to compositions comprising at least 80%, at least 90%, at least 95%, at least 97%, at least 98% or at least 99% β-farnesene by weight, based on total weight of the farnesene. In other embodiments, β-farnesene comprises a mixture of stereoisomers, such as s-cis and s-trans isomers. In some embodiments, the amount of each of the stereoisomers in a β-farnesene mixture is independently from about 0.1 wt.% to about 99.9 wt.%, from about 0.5 wt.% to about 99.5 wt.%, from about 1 wt.% to about 99 wt.%, from about 5 wt.% to about 95 wt.%, from about 10 wt.% to about 90 wt.%, or from about 20 wt.%) to about 80 wt.%, based on the total weight of the β-farnesene mixture of stereoisomers.

[056] "Farnesane" refers to a compound having the following structure:

or a stereoisomer thereof.

[057] "β-springene" or "springene" refers to a compound having the following structure:

or a stereoisomer thereof.

[058] "Geranylfarnesene" refers to a compound having the following structure:

or a stereoisomer thereof.

[059] "Neophytadiene" refers to a compound having the following structure: or a stereoisomer thereof.

[060] "7>a/75-phyta-l,3-diene" refers to a compound having the following structure:

or a stereoisomer (e.g., s-cis isomer) thereof.

[061] "Cz5-phyta-l,3-diene" refers to a compound having the following structure:

or a stereoisomer (e.g., s-cis isomer) thereof.

[062] "Isodehydrosqualene" refers to a compound having the following structure:

or a stereoisomer thereof.

[063] "Isosqualane precursor I" or "2,6,18,22-tetramethyl-10-methylene-14- vinyltricosa-2, 6,11,17,21 -pentaene" refers to a compound having the following structure:

or a stereoisomer thereof.

[064] "Isosqualane precursor Π" or "2,6,14,18,22-pentamethyl-10-vinyltricosa-

2,6, 10, 14, 17,21 -pentaene" refers to a compound having the following structure:

or a stereoisomer thereof.

[065] "Farnesol" refers to a compound having the following structure:

or a stereoisomer thereof.

[066] "Nerolidol" refers to a compound having the following structure:

or a stereoisomer thereof.

[067] Farnesol or nerolidol may be converted into a-farnesene or β-farnesene, or a combination thereof by dehydration with a dehydrating agent or an acid catalyst. Any suitable dehydrating agent or acid catalyst that can convert an alcohol into an alkene may be used. Non- limiting examples of suitable dehydrating agents or acid catalysts include phosphoryl chloride, anhydrous zinc chloride, phosphoric acid, and sulfuric acid.

[068] A "polymer" refers to any kind of synthetic or natural oligomer or polymer having two or more repeat units, including thermoplastics, thermosets, elastomers, polymer blends, polymer composites, synthetic rubbers, and natural rubbers. A synthetic oligomer or polymer can be prepared by polymerizing monomers, whether of the same or a different type. The generic term "polymer" embraces the terms "homopolymer," "copolymer," "terpolymer" as well as "interpolymer."

[069] "Interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. The generic term "interpolymer" includes the term "copolymer" (which generally refers to a polymer prepared from two different monomers) as well as the term "terpolymer" (which generally refers to a polymer prepared from three different types of monomers). It also encompasses polymers made by polymerizing four or more types of monomers.

[070] "Hydrocarbyl" refers to a group containing one or more carbon atom backbones and hydrogen atoms, and the group may optionally contain one or more heteroatoms. Where the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups known to one of skill in the art. Hydrocarbyl groups may contain cycloaliphatic, aliphatic, aromatic, or any combination thereof. Aliphatic segments may be straight or branched. Aliphatic and cycloaliphatic groups may include one or more double and/or triple carbon-carbon bonds. Included in hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cyclalkyl, cycloalkenyl, alkaryl and aralkyl groups. Cycloaliphatic groups may contain both cyclic moieties and noncyclic portions. In some embodiments, the hydrocarbyl group is a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted C1-C30 hydrocarbyl group (e.g., C1-C20 alkyl, C1-C20 alkenyl, C1-C20 alkynyl, cycloalkyl, aryl, aralkyl and alkaryl). [071] "Alkyl" refers to a group having the general formula C_nH2_n+i derived from a saturated, straight chain or branched aliphatic hydrocarbon, where n is an integer. In certain embodiments, n is from 1 to about 30, from 1 to about 20, or from 1 to about 10. Non-limiting examples of alkyl groups include Ci-C₈ alkyl groups such as methyl, ethyl, propyl, isopropyl, 2- methylpropyl, 2-methylbutyl, 3-methylbutyl, 2,2,-dimethylpropyl, 2-methylpentyl, 3- methylpentyl, 4-methylpentyl, 2-2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-butyl, isobutyl, tert-butyl, isopentyl, n-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n- octyl, isooctyl, n-nonyl, isononyl, n-decyl and isodecyl. An alkyl group may be unsubstituted, or may be substituted. In some embodiments, the alkyl group is straight chain having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbons. In some embodiments, the alkyl group is branched having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbons.

[072] "Cycloaliphatic" encompasses "cycloalkyl" and "cycloalkenyl." Cycloaliphatic groups may be monocyclic or polycyclic. A cycloaliphatic group can be unsubstituted or substituted with one or more suitable substituents.

[073] "Cycloalkyl" refers to a saturated carbocyclic mono- or bicyclic (fused or bridged) ring of 3-12 (e.g., 5-12) carbon atoms. Non-limiting examples of cycloalkyl include C₃-C₈ cycloalkyl groups, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups and saturated cyclic and bicyclic terpenes. Cycloalkyl groups may be unsubstituted or substituted.

[074] "Cycloalkenyl" refers to a non-aromatic carbocyclic mono- or bicyclic ring of 3 to 12 {e.g., 4 to 8) carbon atoms having one or more double bonds. Non-limiting examples of cycloalkenyl include C₃-C₈ cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and unsaturated cyclic and bicyclic terpenes. Cycloalkenyl groups may be unsubstituted or substituted.

[075] "Aryl" refers to an organic radical derived from a monocyclic or polycyclic aromatic hydrocarbon by removing a hydrogen atom. Non-limiting examples of the aryl group include phenyl, naphthyl, benzyl, or tolanyl group, sexiphenylene, phenanthrenyl, anthracenyl, coronenyl, and tolanylphenyl. An aryl group can be unsubstituted or substituted with one or more suitable substituents. Furthermore, the aryl group can be monocyclic or polycyclic. In some embodiments, the aryl group contains at least 6, 7, 8, 9, or 10 carbon atoms. As used herein, one or more dashed bonds in a structure independently represents a bond that may or may not be present. For example, the dashed bond in the structure indicates a bond that may be present to result in a double bond, or may not be present to result in a single bond.

[076] "Isoprenoid" and "isoprenoid compound" are used interchangeably herein and refer to a compound derivable from isopentenyl diphosphate.

[077] A substituted group or compound refers to a group or compound in which at least one hydrogen atom is replaced with a substituent chemical moiety. A substituent chemical moiety may be any suitable substituent that imparts desired properties to the compound or group. Non-limiting examples of substituents include halo, alkyl, heteroalkyl, alkenyl, alkynyl, aryl, heteroayrl, hydroxyl, alkoxyl, amino, nitro, thiol, thioether, imine, cyano, amido, phosphonato, phosphine, carbosyl, thiocarbonyl, sulfonyl, sulfonamide, carbonyl, formyl, carbonyloxy, oxo, haloalkyl (e.g., trifluoromethyl or trichloromethyl), carbocyclic cycloalkyl (which may be monocyclic, or fused or non-fused polycyclic) such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or a heterocycloalkyl (which may be monocyclic, or fused or nonfused polycyclic such as pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl or thiazinyl), carbocyclic or heterocyclic, monocyclic or fused or nonfused polycyclic aryl (e.g., phenyl, naphthyl, pyrrolyl, idolyl, furanyl, thiopenyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, trizolyl, tetrazolyl, pyrazolyl, pyridinyl, quinolinyl, benzothiophenyl, or benzofuranyl); amino (primary, secondary or tertiary): -CONH₂; -OCH₂CONH₂; -NH₂; -S0₂NH₂; -OCHF₂; CF₃, -CC1₃; -OCF₃; - NH₂; -NH(alkyl); -N(alkyl)₂; -NH(aryl); -N(alkyl)(aryl); -N(aryl)₂; -CHO; -CO(alkyl); - CO(aryl); -(OCH₂CH₂0)_n-, where n is from 1 to about 30 (e.g., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 or 20); -(OCH₂CH(CH₃)0)_m-, where m is from 1 to about 30 (e.g., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 or 20); -CI, -Br, or -I; and -C0₂(alkyl) (e.g., -C0₂CH₃ or -C0₂CH₂CH₃; -C0₂(aryl)). In certain embodiments, the substituents disclosed herein may be further substituted with one or more substituents.

[078] As used herein, "detergent" refers to an agent or composition that is useful for cleaning surfaces or articles. A detergent may lift or remove soil, food, oil, grease and the like from a surface (e.g., fabric or a hard surface) and/or disperse or solubilize particles in a medium (e.g., disperse or suspend oil particles in an aqueous solution). A detergent can be in any form, liquid, paste, gel, or solid (e.g., powder, a granular solid, bar, or tablet).

B) Source of Conjugated Hydrocarbon Terpenes [079] The conjugated terpenes disclosed herein may be obtained from any suitable source. In some embodiments, the conjugated terpene is obtained from naturally occurring plants or marine species. For example, farnesene can be obtained or derived from naturally occurring terpenes that can be produced by a variety of plants, such as Copaifera langsdorfii, conifers, and spurges; or by insects, such as swallowtail butterflies, leaf beetles, termites, or pine sawflies; and marine organisms, such as algae, sponges, corals, mollusks, and fish. Terpene oils can also be obtained from conifers and spurges. Conifers belong to the plant division Pinophya or Coniferae and are generally cone -bearing seed plants with vascular tissue. Conifers may be trees or shrubs. Non-limiting examples of suitable conifers include cedar, cypress, douglas fir, fir, juniper, kauris, larch, pine, redwood, spruce and yew. Spurges, also known as Euphorbia, are a diverse worldwide genus of plants belonging to the spurge family (euphorbiaceae).

Farnesene is a sesquiterpene, a member of the terpene family, and can be derived or isolated from terpene oils for use as described herein. In some embodiments, a conjugated terpene is derived from a fossil fuel (petroleum or coal), for example, by fractional distillation of petroleum or coal tar. In some embodiments, a conjugated terpene is made by chemical synthesis. For example, one non-limiting example of suitable chemical synthesis of farnesene includes dehydrating nerolidol with phosphoryl chloride in pyridine as described in the article by Anet E.F.L.J., "Synthesis of (Ε,Ζ)-α-, and (Ζ)-β -farnesene, Aust. J. Chem. 23(10), 2101-2108, which is incorporated herein by reference in its entirety.

[080] In some embodiments, a conjugated terpene is obtained using genetically modified organisms that are grown using renewable carbon sources (e.g., sugar cane). In certain embodiments, a conjugated terpene is prepared by contacting a cell capable of making a conjugated terpene with a suitable carbon source under conditions suitable for making a conjugated terpene. Non-limiting examples conjugated terpenes obtained using genetically modified organisms are provided in U.S. Pat. No. 7,399,323, U.S. Pat. Publ. Nos. 2008/0274523 and 2009/0137014, and International Patent Publication WO 2007/140339, and International Patent Publication WO 2007/139924, each of which is incorporated herein by reference in its entirety. Any carbon source that can be converted into one or more isoprenoid compounds can be used herein. In some embodiments, the carbon source is a fermentable carbon source (e.g., sugars), a nonfermentable carbon source or a combination thereof. A non-fermentable carbon source is a carbon source that cannot be converted by an organism into ethanol. Non-limiting examples of suitable non-fermentable carbon sources include acetate, glycerol, lactate and ethanol. [081] The sugar can be any sugar known to one of skill in the art. For example, in some embodiments, the sugar is a monosaccharide, disaccharide, polysaccharide or a

combination thereof. In certain embodiments, the sugar is a simple sugar (a monosaccharide or a disaccharide). Some non-limiting examples of suitable monosaccharides include glucose, galactose, mannose, fructose, ribose and combinations thereof. Some non-limiting examples of suitable disaccharides include sucrose, lactose, maltose, trehalose, cellobiose, and combinations thereof. In some embodiments, the sugar is sucrose. In certain embodiments, the carbon source is a polysaccharide. Non-limiting examples of suitable polysaccharides include starch, glycogen, cellulose, chitin, and combinations thereof.

[082] The sugar suitable for making a conjugated terpene can be obtained from a variety of crops or sources. Non- limiting examples of suitable crops or sources include sugar cane, bagasse, miscanthus, sugar beet, sorghum, grain sorghum, switchgrass, barley, hemp, kenaf, potato, sweet potato, cassava, sunflower, fruit, molasses, whey, skim milk, corn, stover, grain, wheat, wood, paper, straw, cotton, cellulose waste, and other biomass. In certain embodiments, suitable crops or sources include sugar cane, sugar beet and corn. In some embodiments, the sugar source is cane juice or molasses.

[083] In certain embodiments, a conjugated terpene can be prepared in a facility capable of biological manufacture of isoprenoids. For example, for making a C₁₅ isoprenoid, the facility may comprise any structure useful for preparing C₁₅ isoprenoids (e.g. , a-farnesene, β- farnesene, nerolidol or farnesol) using a microorganism capable of making the C₁₅ isoprenoids with a suitable carbon source under conditions suitable for making the C₁₅ isoprenoids. In some embodiments, the biological facility comprises a cell culture comprising a desired isoprenoid (e.g. , a Cio, a C₁₅, a C₂o, a C₂₅, or a C30 isoprenoid) in an amount of at least about 1 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 20 wt.%, or at least about 30 wt.%, based on the total weight of the cell culture. In certain embodiments, the biological facility comprises a fermentor comprising one or more cells capable of generating a desired isoprenoid. Any fermentor that can provide for cells or bacteria a stable and optimal environment in which they can grow or reproduce may be used herein. In some embodiments, the fermentor comprises a culture comprising one or more cells capable of generating a desired isoprenoid (e.g. , a C₁₀, a Ci5, a C₂o, or a C₂₅ isoprenoid). In some embodiments, the fermentor comprises a cell culture capable of biologically manufacturing farnesyl pyrophosphate (FPP). In certain embodiments, the fermentor comprises a cell culture capable of biologically manufacturing isopentenyl diphosphate (IPP). In some embodiments, the fermentor comprises a cell culture comprising a desired isoprenoid (e.g., a C₁₀, a C₁₅, a C20, or a C25 isoprenoid) in an amount of at least about 1 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 20 wt.%, or at least about 30 wt.%, based on the total weight of the cell culture.

[084] The facility may further comprise any structure capable of manufacturing a chemical derivative from the desired isoprenoid (e.g., a C₁₀, a C₁₅, a C20, a C25 or a C30 isoprenoid). In some embodiments, a facility comprises a reactor for dehydrating nerolidol or farnesol to a-farnesene or β-farnesene or a combination thereof. In certain embodiments, a facility comprises a reactor for dehydrating linalool to myrcene or ocimene or a combination thereof. Any reactor that can be used to convert an alcohol into an alkene under conditions known to skilled artisans may be used. In some embodiments, the reactor comprises a dehydrating catalyst.

C) Formation of Diels- Alder Adducts

[085] Described herein are Diels-Alder adducts of conjugated terpenes and a dienophile, and derivatives of such Diels-Alder adducts. In a Diels-Alder reaction between a conjugated terpene and a dienophile, a [2π + 4π] cycloaddition reaction between the conjugated diene moiety of the conjugated terpene and the dienophile occurs. In some cases, the stereochemistry of the resulting compounds can be reliably predicted using orbital symmetry rules. In certain embodiments, a Diels-Alder reaction between a conjugated terpene and a dienophile is thermally driven, without the need for a catalyst. In some embodiments, a Diels- Alder reaction occurs at a temperature in a range from about 50 °C to about 100 °C, or from about 50 °C to about 130 °C. In other embodiments, a catalyst is used, e.g., to increase reaction rate, to increase reactivity of weak dienophiles or sterically hindered reactants, or to increase selectivity of certain adducts or isomers. For example, a Lewis acid catalyst may be used in some variations. In some embodiments, a Diels-Alder reaction is run without solvent. In certain embodiments, reaction conditions (e.g., temperature, pressure, catalyst (if present), solvent (if present), reactant purities, reactant concentrations relative to each other, reactant concentrations relative to a solvent (if present), reaction times and/or reaction atmosphere are selected so that formation of dimers, higher oligomers and/or polymers of the conjugated terpene is suppressed or minimized. Reaction conditions (e.g., temperature, pressure, catalyst (if present), solvent (if present), reactant purities, reactant concentrations relative to each other, reactant concentrations relative to a solvent (if present), reaction times and/or reaction atmosphere may be selected so that formation of dimers, higher oligomers and/or polymers of the diene is suppressed or minimized. In some embodiments, the reaction conditions (e.g., temperature, catalyst (if present), solvent (if present), reactant purities, reactant concentrations, reaction times, reaction atmosphere and/or reaction pressure are selected to produce a desired adduct or isomer. More detailed descriptions of the Diels-Alder reaction and reaction conditions for the Diels-Alder reaction are disclosed in the book by Fringuelli et al., titled "The Diels-Alder Reaction: Selected Practical Methods," 1st edition, John Wiley & Sons, Ltd., New York (2002), which is incorporated by reference herein in its entirety. Non- limiting Diels-Alder reactions using β- farnesene to produce pheromones are provided in U.S. Patent No. 4,546,110, which is incorporated herein by reference in its entirety.

[086] A variety of electron deficient dienophiles may effectively undergo the Diels-

Alder reaction with conjugated terpenes to produce cyclic compounds that have utility as surfactants. Any dienophile that can undergo the Diels-Alder reaction with one or more dienes may be used herein. Some non-limiting examples of suitable dienophiles are disclosed in Fringuelli et al., titled "The Diels-Alder Reaction: Selected Practical Methods," 1st edition, John Wiley & Sons, Ltd., New York, pages 3-5 (2002), which is incorporated herein. Other non- limiting examples of dienophiles are provided in Section D below. Any conjugated terpene described herein or otherwise known may undergo Diels-Alder reaction with a dienophile to provide a Diels-Alder adduct having utility as a surfactant. Some non-limiting examples of conjugated hydrocarbon terpenes that may be used to make the Diels-Alder adducts are provided in Section E below and include myrcene, ocimene, a-farnesene, β-farnesene, β-springene, geranylfarnesene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II. Some non-limiting examples of Diels-Alder adducts are provided in Section F below. Non- limiting examples of chemical modifications for Diels-Alder adducts are provided in Section G below.

D) Dienophiles

[087] The dienophile used herein can be any dienophile that undergoes a Diels-Alder reaction with a diene on the conjugated hydrocarbon terpene to form the corresponding cyclic compound. In certain embodiments, the dienophile has formula (I), (II) or (III):

wherein each of R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ is independently H, a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted C₁-C₃₀ hydrocarbyl group (e.g., C_\- C₂₀ alkyl, C₁-C₂₀ alkenyl, C₁-C₂₀ alkynyl, cycloalkyl, aryl, aralkyl and alkaryl), hydroxyalkyl (e.g., -CH₂OH), aminoalkyl (e.g., -CH₂NH₂), carboxylalkyl (e.g., -CH₂C0₂H), thioalkyl

(e.g., -CH₂SH), epoxyalkyl (e.g., glycidyl), hydroxyaryl, aminoaryl, carboxylaryl, thioaryl, hydroxyl, amino, halo, cyano, nitro, sulfonate, sulfmate, sulfoxide, acyl (e.g., formyl and acetyl), -CO₂R¹⁹, -(CH₂)_nC0₂R²⁰, -COO Mi⁺, -(CH₂)_mCOO M₂ ⁺, -C(=0)NR²¹R²², -OR²³ or -C(=0)X where X is halo; or R¹¹ and R¹² together or R¹³ and R¹⁴ together form a -C(=0)-0-C(=0)- group, a -C(=0)-S-C(=0)- group, a -C(=0)-NR²⁴-C(=0)- group, a -C(=0)-CR²⁵=CR²⁶-C(=0)- group, or a -C(=0)-C(=0)-CR²⁷=CR²⁸- group; or R¹¹ and R¹³ together or R¹² and R¹⁴ together form a -CH₂-C(=0)-0-C(=0)- group, where each of Mi⁺ and M₂ ⁺ is independently a

monovalent cation such as Fr⁺, Cs⁺, Rb⁺, K⁺, Na⁺, Li⁺, Ag⁺, Au⁺, Cu⁺, NH₄ ⁺, primary

ammonium, secondary ammonium, tertiary ammonium, or quaternary ammonium; each of R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ is independently H, hydrocarbyl, hydroxyalkyl, aminoalkyl, carboxylalkyl, thioalkyl, epoxyalkyl, hydroxyaryl, aminoaryl, carboxylaryl,

25 26 27 28 thioaryl, hydroxyl, amino, halo, cyano, nitro or acyl, or R and R together or R and R together form a benzo ring or a substituted or unsubstituted -CH₂(CH₂)_kCH₂- group; and each of m, n and k is independently an interger from 1 to 20 or from 1 to 12, with the proviso that at least one of R¹¹, R¹², R¹³ and R¹⁴ is not H, and the proviso that at least one of R¹⁵ and R¹⁶ is not

17 18

H, and the proviso that at least one of R and R is not H.

In some embodiments, a dienophile has formula (Al), (A2), (A3), (A4), (A5),

4),

(A7), wherein QA¹ may be O, S, or NRA¹⁹; each of QA², QA³ and QA⁴ may independently be a halo

20 21 22 5

substituent (e.g., chloro or bromo), NRA RA or ORA ; QA may be a halo substituent (e.g., chloro or bromo), a cyano group or ORA²³; and each of RA¹, RA², RA³, RA⁴, RA⁵, RA⁶, RA⁷, RA⁸, RA⁹, RA¹⁰, RA¹¹, RA¹², RA¹³, RA¹⁴, RA¹⁵, RA¹⁶, RA¹⁷, RA¹⁸, RA¹⁹, RA²⁰, RA²¹, RA²²

23

and RA is independently H, C1-C20 alkyl, C1-C20 alkenyl, C1-C20 alkynyl, cycloalkyl, aryl, aralkyl, alkaryl, OH, NH₂, sulfonate, sulfinate, sulfoxide, carboxyl, epoxy or glycidyl.

[089] In some embodiments, the dienophile comprises an unsaturated carbon-carbon bond with one or more electron withdrawing groups attached to a carbon of the unsaturated bond. Non-limiting examples of electron withdrawing groups that may be attached to an unsaturated carbon-carbon bond in a dienophile include: one or more substituted carbonyl groups such as one or more ester groups represented as -COOR, one or more aldehyde groups represented as -CHO, one or more ketone groups represented as -COR, one or more carboxyl groups represented as -COOH, one or more amide groups represented as -CONRR', one or more imide groups represented as -CONRCOR', one or more aryloxycarbonyl groups such as a phenoxycarbonyl group, one or more carbonyloxycarbonyl groups, or a one or more

carbonyliminocarbonyl groups, wherein each of R and R' is independently H or any C1-C30 aliphatic, aromatic, linear, branched, cyclic or acyclic, substituted or unsubstituted, saturated or unsaturated hydrocarbyl group, and may include one or more heteroatoms such as nitrogen, oxygen, phosphorus, sulfur, or chloride. In some embodiments, the dienophile comprises a vinyl sulfonate, vinyl sulfinate, or vinyl sulfoxide.

[090] In certain embodiments, the dienophile comprises sulfur dioxide, or a sulfone

S0₂RR', where R and R' may independently be any C1-C30 hydrocarbyl group.

[091] Some non-limiting examples of suitable dienophiles that can form Diels-Alder adducts with conjugated terpenes (e.g., farnesene or myrcene) include acrolein, acrylic acid, acrylate esters, vinyl ketones, dialkyl maleates, dialkyl fumarates, maleic anhydride, itaconic acid, maleimides, fumaronitrile, malononitrile, acetylene dicarboxylic acids, and acetylene dicarboxylic acid esters.

[092] Some non-limiting specific examples of dienophiles that can react with a conjugated terpene (e.g., farnesene or myrcene) to produce a compound useful as described herein include dienophiles in groups (A)-(Y) below:

(A) maleic anhydride and substituted maleic anhydrides;

(B) citraconic anhydride and substituted citraconic anhydrides;

(C) itaconic acid and substituted itaconic acids; (D) itaconic anhydride and substituted itaconic anhydrides;

(E) acrolein and substituted acroleins;

(F) crotonaldehyde and substituted crotonaldehydes;

(G) dialkyl maleates or dialkyl fumarates (e.g., linear or branched, cyclic or acyclic, Ci- C30 dialkyl maleates or dialkyl fumarates such as dimethyl maleate, dimethyl fumarate, diethyl maleate, diethyl fumarate, di-n-propyl maleate, di-n-propyl fumarate, di-isopropyl maleate, di- isopropyl fumarate, di-n-butyl maleate, di-n-butyl fumarate, di(isobutyl) maleate, di(isobutyl) fumarate, di-tert-butyl maleate, di-tert butyl fumate, di-n-pentyl maleate, di-n-pentyl fumarate, di(isopentyl) maleate, di(isopentyl) fumarate, di-n-hexyl maleate, di-n-hexyl fumarate, di(2- ethylhexyl) maleate, di(2-ethylhexyl) fumarate, di(isohexyl) maleate, di(isohexyl) fumarate, di- n-heptyl maleate, di-n-heptyl fumarate, di(isoheptyl) maleate, di(isoheptyl) fumarate, ,di-n-octyl maleate, di-n-octyl fumarate, di(isooctyl) maleate, di(isooctyl) fumarate, di-n-nonyl maleate, di- n-nonyl fumarate, di(isononyl) maleate, di(isononyl) fumarate, di-n-decyl maleate, di-n-decyl fumarate, di(isodecyl) maleate), and di(isodecyl) fumarate;

(H) dialkyl itaconates (e.g., linear or branched, cyclic or acyclic, C₁-C30 dialkyl itaconates such as dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-isopropyl itaconate, di-n-butyl itaconate, di(isobutyl) itaconate, di-tert-butyl itaconate, di-n-pentyl itaconate, di(isopentyl) itaconate, di-n-hexyl itaconate, di(2-ethylhexyl) itaconate, di(isohexyl) itaconate, di-n-heptyl itaconate, di(isoheptyl) itaconate, di-n-octyl itaconate, di(isooctyl) itaconate, di-n-nonyl itaconate, di(isononyl) itaconate, di-n-decyl itaconate and di(isodecyl) itaconate);

(I) acrylic acid esters (e.g., linear or branched, cyclic or acyclic, C₁-C30 alkyl acrylates, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, isohexyl acrylate, 2-ethylhexyl acrylate, n-heptyl acrylate, isoheptyl acrylate, n-octyl acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl acrylate, isodecyl acrylate, n-undecyl acrylate, isoundecyl acrylate, n-dodecyl acrylate, isododecyl acrylate, n-tridecyl acrylate, n- tetradecyl acrylate, n-pentadecyl acrylate, n-hexadecyl acrylate, n-heptadecyl acrylate, n- octadecyl acrylate, n-nonadecyl acrylate, n-eicosyl acrylate, and n-tricosyl acrylate);

(J)methacrylic acid esters (e.g., linear or branched, cyclic or acyclic, C₁-C30 alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, 2-ethylhexyl methacrylate, n-heptyl methacrylate, isoheptyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, n- nonyl methacrylate, isononyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, n- undecyl methacrylate, isoundecyl methacrylate, n-dodecyl methacrylate, isododecyl

methacrylate, n-tridecyl methacrylate, n-tetradecyl methacrylate, n-pentadecyl methacrylate, n- hexadecyl methacrylate, n-heptadecyl methacrylate, n-octadecyl methacrylate, n-nonadecyl methacrylate, n-eicosyl methacrylate, and n-tricosyl methacrylate);

(K)cinnamic acid and cinnamic acid esters (e.g., linear or branched, cyclic or acyclic, C₁-C30 alkyl cinnamate, such as methyl cinnamate and ethyl cinnamate);

(L)mesityl oxide and substituted mesityl oxides;

(M)hydroxyalkyl acrylates (e.g., 2-hydroxymethyl acrylate and 2 -hydroxy ethyl acrylate);

(N)carboxy alkyl acrylates (e.g., 2-carboxyethyl acrylate);

(0)(dialkylamino)alkyl acrylates (e.g., 2-(diethylamino)ethyl acrylate);

(P)dialkyl acetylene dicarboxylates (e.g., linear or branched, cyclic or acyclic, C₁-C30 dialkyl acetylene dicarboxylates such as dimethyl acetylene dicarboxylate, diethyl acetylene dicarboxylate, di-n-propyl acetylene dicarboxylate, di(isopropyl) acetylene dicarboxylate, di-n- butyl acetylene dicarboxylate, di(isobutyl) acetylene dicarboxylate, di(tert-butyl) acetylene dicarboxylate, di-n-pentyl acetylene dicarboxylate, di(isopentyl) acetylene dicarboxylate, di-n- hexyl acetylene dicarboxylate, di(2-ethylhexyl) acetylene dicarboxylate, di(isohexyl) acetylene dicarboxylate, di-n-heptyl acetylene dicarboxylate, di(isoheptyl) acetylene dicarboxylate, di-n- octyl acetylene dicarboxylate, di(isooctyl) acetylene dicarboxylate, di-n-decyl acetylene dicarboxylate, and di(isodecyl) acetylene dicarboxylate);

(Q)vinyl ketones (e.g., linear or branched, cyclic or acyclic, aliphatic or aromatic, C₁-C30 vinyl ketones, such as methyl vinyl ketone, ethyl vinyl ketone, n-propyl vinyl ketone, n-butyl vinyl ketone, isobutyl vinyl ketone, tert-butyl vinyl ketone, n-pentyl vinyl ketone, n-hexyl vinyl ketone, 2-ethylhexyl vinyl ketone, n-heptyl vinyl ketone, n-octyl vinyl ketone, n-nonyl vinyl ketone, n-decyl vinyl ketone, n-undecyl vinyl ketone, n-dodecyl vinyl ketone, n-tridecyl vinyl ketone, n-tetradecyl vinyl ketone, n-pentadecyl vinyl ketone, n-hexadecyl vinyl ketone, n- heptadecyl vinyl ketone, n-octadecyl vinyl ketone, n-nonadecyl vinyl ketone, n-eicosyl vinyl ketone, and n-tricosyl vinyl ketone);

(R)maleimide and substituted maleimides (e.g., linear or branched, cyclic or acyclic, C_\- C30 alkyl N-substituted maleimides, such as N-methylmaleimide, N-ethyl maleimide, N-n- propyl maleimide, N-isopropyl maleimide, N-n-butyl maleimide, N-tert-butyl maleimide, N-n- pentyl maleimide, N-isopentyl maleimide, N-n-hexyl maleimide, N-isohexyl maleimide, N-(2- ethylhexyl) maleimide, N-n-heptyl maleimide, N-n-octyl maleimide, N-n-decyl maleimide, N-n- undecyl maleimide, N-n-dodecyl maleimide, N-n-tridecyl maleimide, N-n-tetradecyl maleimide, N-n-pentadecyl maleimide, N-n-hexadecyl maleimide, N-n-heptadecyl maleimide, N-n- octadecyl maleimide, N-n-nonadecyl maleimide, N-n-eicosyl maleimide, and maleimides in which the nitrogen is substituted with -COOR, where R represents any linear or branched, cyclic or acyclic C₁-C30 alkyl group, for example, N-methoxycarbonylmaleimide);

(S)dialkyl azidocarboxylates, e.g. linear or branched, cyclic or acyclic, C₁-C30 dialkyl azidocarboxylates, such as dimethyl azidocarboxylate, and diethyl azidocarboxylate;

(T)azidocarboxylic acid and azidodicarboxylic acid diesters containing two ester groups which may be the same or different ester groups;

(U)sulfur dioxide;

(V) 1 ,4-benzoquinone and substituted 1,4-benzoquinones {e.g., 2-(3-methyl-2- butenyl)benzo-l,4-quinone), 1 ,2-benzoquinone and substituted 1 ,2-benzoquinones;

(W)naphthoquinones such as 1,4-naphthoquinone, 1 ,2-naphthoquinone, plumbagin

andjuglone (X)phosphorus trihalide {e.g., phosphorus tribromide); and

(Y)vinyl sulfonates, vinyl sulfmates, or vinyl sulfoxides. E) Conjugated Hydrocarbon Terpenes

[093] The conjugated hydrocarbon terpene used herein can be any conjugated hydrocarbon terpene having a diene group that undergoes a Diels-Alder reaction with a dienophile to form the corresponding cyclic compound. In certain embodiments, the conjugated hydrocarbon terpene has formula (IV):

wherein each of RB¹, RB², RB³ and RB⁴ is independently H, a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted C1-C30 hydrocarbyl group, with the proviso that at least one of RB¹, RB², RB³ and RB⁴ is not hydrogen.

[094] The hydrocarbon terpene is selected to have a stereochemistry amenable to Diels-

Alder reactions. That is, the conjugated diene is able to adopt an s-cis conformer. For a hydrocarbon terpene to undergo Diels-Alder cycloaddition reaction, the double bonds exist in an s-cis conformation or conformational rotation around the single bond between the double bonds so that an s-cis conformation of the diene is adoptable. In many conjugated dienes, the s-trans conformer population is in rapid equilibrium with s-cis conformers. In some cases, steric effects due to substituents on the conjugated diene may impede a Diels-Alder reaction. In some cases, hydrocarbon terpenes having terminal conjugated diene groups are selected, i.e., hydrocarbon terpenes in which RB¹, RB², and RB³ are each H, but RB⁴ is not H. In some cases, RB¹ is H, but RB², RB³ and RB⁴ are not H. In some cases, RB¹ and RB² are H, but RB³ and RB⁴ are not H.

[095] In some embodiments, the conjugated hydrocarbon terpene has formula (IV) where each of RB¹, RB³ and RB⁴ is independently H; and RB² has formula (V):

wherein n is 1, 2, 3 or 4. In some embodiments, the conjugated hydrocarbon terpene has formula (AI):

wherein n is 1, 2, 3 or 4.

[096] In certain embodiments, the conjugated hydrocarbon terpene is myrcene which has formula (AI) where n is 1. In some embodiments, the conjugated hydrocarbon terpene is β- farnesene which has formula (AI) where n is 2. In certain embodiments, the conjugated hydrocarbon terpene is β-springene which has formula (AI) where n is 3. In some embodiments, the conjugated hydrocarbon terpene is geranylfarnesene which has formula (AI) where n is 4.

[097] In certain embodiments, the conjugated hydrocarbon terpene has formula (IV) where each of RB³ and RB⁴ is H; RB² is methyl; and RB¹ has formula (VI):

wherein m is 1, 2, 3 or 4. The dashed bond in formula (VI) represents a bond that may be present to result in a double bond, or may not be present to result in a single bond. In other embodiments, the conjugated hydrocarbon terpene has formula (All):

wherein m is 1, 2, 3 or 4.

[098] In certain embodiments, the conjugated hydrocarbon terpene is β-ocimene which has formula (All) where m is 1. In some embodiments, the conjugated hydrocarbon terpene is a-farnesene which has formula (All) where m is 2.

[099] In some embodiments, the conjugated hydrocarbon terpene that can react with a dienophile disclosed herein is isodehydrosqualene. In certain embodiments, the conjugated hydrocarbon terpene is isosqualane precursor I. In some embodiments, the hydrocarbon terpene is isosqualane precursor II.

F) Diels-Alder Adducts

[0100] Diels-Alder adducts can be prepared by reacting a dienophile disclosed herein with one or more conjugated hydrocarbon terpene under Diels-Alder reaction condition with or without the presence of a catalyst. The hydrocarbon terpene and a dienophile in a Diels-Alder reaction may each demonstrate stereoisomerism. Stereoisomerism of the reactants is preserved in the Diels-Alder adduct, and the relative orientation of the substituents on the reactants is preserved in the Diels-Alder adduct. For example, fumaric acid and fumaric acid esters (fumarate) exist as trans -isomers, so if a fumaric acid ester is used a dienophile, the carboxylate groups in the Diels-Alder adduct have a 1 ,2-anti- (also referred to as trans-) orientation relative to each other. The carboxylate groups (or anhydride) of maleic anhydride, maleic acid, and maleic acid esters (maleates) have a cis- orientation, so that the carboxylate groups in the Diels- Alder adduct have a 1 ,2-syn- (also referred to as cis-) orientation relative to each other.

[0101] In some embodiments, a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (I) to provide the Diels-Alder adduct having formula (VIIA) or (VIIB) or a mixture thereof:

wherein RB¹, RB², RB³, RB⁴, R¹¹, R¹², R¹³ and R¹⁴ are as defined herein.

[0102] In some embodiments, the Diels-Alder adduct of formula (VIIA) and (VIIB) can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form a hydrogenated adduct having formula (VIIA') and (VIIB') respectively:

wherein RB¹, RB², RB³, RB⁴, R¹¹, R¹², R¹³ and R¹⁴ are as defined herein.

[0103] In certain embodiments, a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (II) to provide the Diels-Alder adduct having formula (VIIIA) or (VIIIB) or a mixture thereof:

(VIIIB) wherein RB¹, RB², RB³, RB⁴, R¹⁵ and R¹⁶ are as defined herein. In some embodiments, the Diels-Alder adduct of formula (VIIA) and (VIIB) can be oxidized by any oxidation reaction known to a skilled artisan to form an oxidized adduct having formula (VIIIA") and (VIIIB"), respectively.

[0104] In some embodiments, the Diels-Alder adduct of formula (VIIIA) and (VIIIB) can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form a hydrogenated adduct having formula (VIIIA') and (VIIIB') respectively:

(VIIIA'), or (VIIIB'), wherein RB¹, RB², RB³, RB⁴, R¹⁵ and R¹⁶ are as defined herein.

[0105] In some embodiments, the Diels-Alder adduct of formula (VIIIA) and (VIIIB) or of formula (VIIA) and (VIIB) can be oxidized by any oxidation reaction known to a skilled artisan to form an oxidized adduct having formula (VIIIA") and (VIIIB"), respectively:

(VIIIA"), or (VIIIB"), wherein RB¹, RB², RB³, RB⁴, R¹⁵ and R¹⁶ are as defined herein.

[0106] In certain embodiments, a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (III) to provide the Diels-Alder adduct having formula (IXA) or (IXB) or a mixture thereof:

wherein RB¹, RB², RB³, RB⁴, R¹⁷ and R¹⁸ are as defined herein.

[0107] In some embodiments, the Diels-Alder adduct of formula (IXA) and (IXB) can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form a hydrogenated adduct having formula (ΙΧΑ') and (ΙΧΒ') respectively:

wherein RB¹, RB², RB³, RB⁴, R¹⁷ and R¹⁸ are as defined herein.

[0108] In some embodiments, each of RB¹, RB³ and RB⁴ of the adduct of formula

(VIIA), (VIIA'), (VIIB), (VIIB'), (VIIIA), (VIIIA'), (VIIIA"), (VIIIB), (VIIIB'), (VIIIB"), (IXA), (ΙΧΑ'), (IXB) or (ΙΧΒ') is independently H; and RB² has formula (X):

wherein n is 1, 2, 3 or 4. In certain embodiments, n is 1. In some embodiments, n is 2. In certain embodiments, n is 3. In some embodiments, n is 4.

[0109] In some embodiments, RB having formula (X) in the adducts disclosed herein can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form the corresponding alkyl group having formula (XI):

wherein n is 1, 2, 3 or 4. In certain embodiments, n is 1. In some embodiments, n is 2. In certain embodiments, n is 3. In some embodiments, n is 4.

[0110] In some embodiments, RB having formula (X) in the adducts disclosed herein can be epoxidized by any epoxidation reaction known to a skilled artisan to form the corresponding epoxy group having formula (XII):

wherein n is 1, 2, 3 or 4. In certain embodiments, n is 1. In some embodiments, n is 2. In certain embodiments, n is 3. In some embodiments, n is 4.

[0111] In certain embodiments, each of RB³ and RB⁴ of the adduct of formula (VIIA),

(VIIA'), (VIIB), (VIIB'), (VIIIA), (VIIIA'), (VIIIA"), (VIIIB), (VIIIB'), (VIIIB"), (IXA), (ΙΧΑ'), (IXB) or (ΙΧΒ') is independently is H; RB² is methyl; and RB¹ has formula (XIII):

wherein m is 1, 2, 3 or 4. In certain embodiments, m is 1. In some embodiments, m is 2. In certain embodiments, m is 3. In some embodiments, m is 4.

[0112] In some embodiments, RB¹ having formula (XIII) in the adducts disclosed herein can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form the corresponding alkyl group having formula (XIV):

wherein m is 1, 2, 3 or 4. In certain embodiments, m is 1. In some embodiments, m is 2. In certain embodiments, m is 3. In some embodiments, m is 4.

[0113] In some embodiments, the Diels-Alder adduct between a conjugated hydrocarbon terpene and a dienophile is represented by formula (Bl):

where RB¹, RB², RB³ and RB⁴ represent the substituents of the conjugated diene of the conjugated terpene and may each independently be H or a C1-C30 saturated or unsaturated, cyclic or acyclic, hydrocarbyl group, with the proviso that one of RB¹, RB², RB³ and RB⁴ is not

1 2

hydrogen. In certain embodiments, QB and QB represent the residue of the dienophile directly following the Diels-Alder reaction. In some embodiments, QB 1 and QB 2 represent the residue following Diels-Alder reaction that has undergone subsequent chemical modification. In certain embodiments, a 6-membered ring adduct is formed by the Diels-Alder reaction. In some embodiments, the Diels-Alder adduct formed comprises a 5-membered ring so that QB¹ and QB are the same. Each of the dashed bonds in formula (Bl) independently represents a bond that may be present to result in a double bond, or may not be present to result in a single bond. In some embodiments, the Diels-Alder adduct is derived form a dienophile containing a double

1 2 2 bond and therefore, the bond between QB and QB is single and the bond between RB and RB is double. In certain embodiments, the Diels-Alder adduct is derived form a dienophile

1 2

containing a triple bond, and therefore, the bond between QB and QB is double and the bond

2 3

between RB and RB is double. In some embodiments, the Diels-Alder adduct is derived form a dienophile containing a double bond and is hydrogenated to saturate the double bond between 2 3

RB and RB to form a single bond. In some embodiments, the Diels-Alder adduct is hydrogenated to saturate all or some of the unsaturated bonds in the ring and/or in one or more

1 2 3 4 1 2

of the RB , RB , RB , RB , QB and QB groups. It should be noted that in some embodiments, a cyclohexenyl ring may be oxidized to form a cyclohex-dienyl ring. In other embodiments, a cyclohexenyl or a cyclohex-dienyl ring may be oxidized so that the ring is aromatic.

[0114] In some embodiments, the Diels-Alder adduct is formed between a conjugated hydrocarbon terpene having formula (AI) and a dienophile disclosed herein and the adduct has

formula (Bl), where each of RB¹, RB³ and RB⁴ is H; and RB² is where n is 1, 2, 3 or 4, as represented by formula (B2) or (B3) or a mixture thereof:

[0115] When the conjugated terpene is β-farnesene, the Diels-Alder adduct may be represented by formula (B2), (B3) or a mixture thereof, wherein n is 2. When the conjugated terpene is myrcene, the Diels-Alder adduct may be represented by formula (B2), (B3) or a mixture thereof, wherein n is 1.

[0116] In some embodiments, the Diels-Alder adduct is formed between a conjugated hydrocarbon terpene having formula (All) and a dienophile disclosed herein and the adduct has

formula (Bl) where each of RB³ and RB⁴ is H; RB² is methyl; and RB¹ is

where m is 1, 2, 3 or 4, as represented by formula (B4), (B5), or a mixture thereof:

[0117] When the conjugated terpene is a-farnesene, the Diels-Alder adduct may be represented by formula (B4), (B5) or a mixture thereof where m is 2. When the conjugated terpene is β-ocimene, the Diels-Alder adduct may be represented by formula (B4), (B5) or a mixture thereof where m is 1.

[0118] Table 1 shows RB¹, RB², RB³ and RB⁴ for exemplary conjugated terpenes, where dashed lines indicate unsaturated olefmic bonds originating from the conjugated terpene that may in some embodiments be completely or partially hydrogenated prior to or subsequent to the

Diels-Alder reaction. Table 2 shows QB 1 and QB 2 for some exemplary dienophiles. For both Tables 1 and 2, it should be noted that isomers may be formed in which RB¹ is reversed with

RB 4 , RB 2 is reversed with RB 3 , and/or QB 1 is reversed with QB 2. The Diels-Alder adduct having formula (Bl) may include any combination of RB¹, RB², RB³ and RB⁴ shown in Table 1 with any combination of QB 1 and QB 2 shown in Table 2. For the compounds in Table 1 and Table 2, RB¹, RB², RB³ and RB⁴ are as defined herein, and RB^1', RB^2', RB^3', and RB^4' are defined as RB¹, RB², RB³ and RB⁴.

Table 1. Some exemplary conjugated terpenes for making Diels-Alder adducts having formula

TABLE 2. SOME NON-LIMITING EXAMPLES OF DIENOPHILES AND DIELS-

ALDER ADDUCTS.

C1-C10 alkyl)

and/or

and/or RB⁴ RB₄

the

[0119] In some embodiments, a Diels-Alder adduct is formed in which two conjugated terpene molecules react with a single dienophile (e.g., a dienophile comprising an acetylenic moiety). Some non-limiting examples are shown as entries 1 1 , 12, 13, 14, 16 and 17 in Table 2. It should be noted that the two conjugated terpenes that react with a single dienophile may be the same or different. For example, the following combinations of conjugated terpenes may react with a single dienophile: 2 myrcene; 2 a-farnesene; 2 β-farnesene; 1 a-farnesene and 1 β- farnesene; 1 myrcene and 1 α-farnesene, 1 myrcene and 1 β-farnesene. In certain embodiments, a Diels-Alder adduct is formed in which one conjugated terpene molecule (e.g., myrcene, a- farnesene, or β-farnesene) and one substituted or unsubstituted conjugated diene molecules (e.g., 1 ,3 -butadiene) is reacted with a single dienophile (e.g., a dienophile comprising an acetylenic moiety).

[0120] Also described herein are Diels-Alder adducts between oligomers (e.g., dimers and trimers) of conjugated terpenes and a dienophile. For example, β-farnesene can be dimerized (e.g., to form isodehydrosqualene, isosqualane precursor I or isosqualane precursor II), trimerized, or oligomerized as described in U.S. Patent Application No. 13/ US 13/1 12,991 , filed May 20, 201 1 , and U.S. Patent Application No. 12/552278, filed Sept. 1 , 2009, or to form cyclic dimers, as described in U.S. Patent Nos. 7,691 ,792 and 7,592,295, all of which are incorporated herein by reference in their entireties. The dimers, trimers and oligomers so formed may contain a conjugated diene, which can undergo Diels-Alder reaction with a dienophile.

G) Chemical Modification Of Diels-Alder Adducts

[0121] In some embodiments, a Diels-Alder adduct between one or more conjugated terpenes and a dienophile as described herein may be chemically modified following the Diels- Alder reaction. The chemical modifications may be selected to tune the applicability to the modified Diels-Alder reaction for use as surfactants as described herein. [0122] For example, any one of or any suitable combination of the following chemical modifications in any suitable order may be made to a Diels-Alder adduct: i) an alkoxycarbonyl group may be reduced to a hydroxymethyl or methyl group; ii) one or more ester groups may be hydrolyzed to a carboxylic acid or a salt thereof; iii) one or more carboxyl groups may be decarboxylated to a hydrogen; iv) an anhydride group may be opened to yield the dicarboxylic acid compound or a salt thereof; iv) an anhydride group may be opened with an amine to produce a compound having a carboxylic acid group and an amide on adjacent carbons; v) reduction of amides to amines; vii) opening of anhydrides with hydrogen peroxide; viii) one or more ester groups on a Diels Alder adduct may undergo transesterification with an alcohol (e.g. a methyl ester may undergo transesterification with a C₈ or longer primary alcohol); ix) a formyl group may be reduced to a methyloyl group; x) a hydroxyl substituent may be alkoxylated to form an alkoxylated substituent (e.g., ethoxylated or propoxylated); xi) one or more double bonds originating from the conjugated terpene can be oxidized (e.g., epoxidized); xii) one or more double bonds originating from the conjugated terpene may be halogenated; xiii) a hydroxyl or ester group may undergo a condensation reaction; xiv) a hydroxyl group or amide group may undergo a condensation reaction; xv) a hydroxyl group or ester group may be sulfated; xvi) an alcohol may be converted to an alkyl halide; xvii) an alkyl halide may be reacted with sodium sulfite to form a sulfonate; xviii) an amine group may be converted to an ammonium ion (e.g., a quaternary ammonium ion) or an amine -oxide; and xix) a reverse Diels-Alder reaction may occur to yield desired products.

[0123] In certain embodiments, a Diels-Alder adduct between a conjugated terpene and a dienophile as described herein is hydrogenated so as to completely or partially hydrogenate aliphatic of the Diels-Alder adduct. Such hydrogenated Diels-Alder adducts (and derivatives thereof) may in certain circumstances exhibit improved thermo-oxidative stability in use.

[0124] In certain embodiments, a ring formed in the Diels-Alder adduct is oxidized. For example, a cyclohexenyl ring may be oxidized to a cyclohexadienyl ring or to an aromatic 6- membered ring, or a cyclohexadienyl ring may be oxidized to an aromatic 6-membered ring.

[0125] In some embodiments, at least one carbon-carbon double bond remains in the aliphatic tail originating from the conjugated terpene in the Diels-Alder adduct. The unsaturated bond may undergo oxidation, e.g., to form a polyol.

[0126] Table 3 illustrates some non-limiting examples of chemical modifications of

Diels-Alder adducts between conjugated terpenes and dienophiles. Table 3. Some exem lary chemical modifications of Diels-Alder adducts.

RB⁴ b RB^{4 0} and/or RB⁴

RB^{4 RB} (reduction)

[0127] In some embodiments, one or more carbon-carbon double bonds of a conjugated terpene Diels- Alder adduct as described herein is oxidized (e.g., epoxidized). Such oxidized (e.g., epoxidized) hydrocarbon terpene derivatives may be useful in a variety of applications. For example, oxidized farnesene derivatives may exhibit increased compatibility or solubility with relatively polar polymers or solvents. In some embodiments, an epoxidized farnesene derivative may be useful as a reactive diluent in a resin and/or as a cross-linking agent. Any suitable oxidation technique known to oxidize carbon-carbon double bonds may be used. For example, any suitable oxidant such as peroxides, peracetic acid, meta chloroperoxybenzoic acid, enzymes, or peroxide complexes such as urea-peroxide complexes (e.g., Novozyme-435™ urea- peroxide complex) may be used. In some embodiments, the oxidation (e.g., epoxidation) conditions are adjusted to oxidize only one carbon-carbon double bond, e.g. , one carbon-carbon double bond that originated in the conjugated terpene starting material. In some embodiments, the oxidation (e.g., epoxidation) conditions are adjusted to oxidize two carbon-carbon double bonds, e.g. , two carbon-carbon double bonds that originated in the conjugated terpene starting material. In some embodiments, oxidation (e.g., epoxidation) conditions are adjusted to oxidize three or more carbon-carbon double bonds, e.g., three or more carbon-carbon double bonds that originated in the conjugated terpene starting material. In some embodiments, oxidation (e.g., epoxidation) conditions are adjusted to oxidize substantially all carbon-carbon double bonds originating in the conjugated terpene starting material. A molar ratio of oxidantxonjugated terpene may be lower than the number of unsaturated carbon-carbon bonds to produce compositions in which not all carbon-carbon double bonds are oxidized (e.g., epoxidized). A molar ratio of oxidantxonjugated terpene may be about 5: 1 or less for farnesene -based compounds, such as about 5: 1, 4: 1, 3: 1, 2: 1, 1 : 1 or 0.5: 1.

[0128] Alcohols and polyols may be derived from epoxidized hydrocarbon terpene

Diels-Alder adducts using any known technique that allows for reaction of epoxy groups to form hydroxyl groups. For example, an epoxy group can be reduced to form a single hydroxyl group, or an epoxy group can be hydrolyzed to form two hydroxyl groups. In some variations, the hydroxyl groups may be subsequently acetylated to form a compound that may have use as described herein.

[0129] In some variations, the alcohols and polyols (e.g., diols) disclosed herein have utility as solvents or surfactants.

[0130] In some embodiments, one or more carbon-carbon double bonds of a conjugated terpene Diels-Alder adduct as described herein is halogenated, e.g., with chlorine where one chlorine atom is added to each double bond using a reagent such as HC1, or where two chlorine atoms are added to each double bond using a reagent such as chlorine gas. Such chloride containing hydrocarbon conjugated terpene derivatives may for example exhibit increased compatibility or solubility with relatively polar polymers or solvents. In some embodiments, the reaction conditions are adjusted such only one carbon-carbon double bond is chlorinated, e.g., one carbon-carbon double bond that originated in the conjugated terpene starting material. In some embodiments, the reaction conditions are adjusted so that two carbon-carbon double bonds are halogenated {e.g., chlorinated), e.g., two carbon-carbon double bonds that originated in the conjugated terpene starting material. In some embodiments, reaction conditions are adjusted such that three or more carbon-carbon double bonds are halogenated {e.g., chlorinated), e.g., three or more carbon-carbon double bonds that originated in the conjugated terpene starting material. In some embodiments, substantially all carbon-carbon double bonds originating from the conjugated terpene are halogenated {e.g., chlorinated).

H) Non-Limiting Examples of Farnesene-Based Diels-Alder Adducts

[0131] Described below in Sections (H-I) - (H-XII) are some non-limiting specific examples of Diels-Alder adducts made using β-farnesene or a-farnesene as the conjugated hydrocarbon terpene. It should be understood that analogs of these examples of Diels-Alder adducts are contemplated in which conjugated terpenes other than a-farnesene or β -farnesene are used. (H-I) Acrylate Ester Dienophiles

[0132] In some embodiments, a Diels-Alder adduct is formed between β-farnesene and

O o acrylic acid, ^{^}OH _{s 0}r an acrylate ester, ^OR _s where R¹ is as described below in connection with formula (H-IA) and (H-IB). A surfactant may be derived from a Diels-Alder adduct between β-farnesene and acrylic acid or an acrylate ester. Diels-Alder adducts formed between β-farnesene and an acrylate ester can be represented by formula (H-IA), (H-IB), and/or an isomer thereof, or a mixture thereof:

where R¹ may be H, or a linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted substituent, e.g., C1-C30 hydrocarbyl. In some embodiments, R¹ is an aliphatic C1-C30 substituent. In some embodiments, R¹ is a linear saturated or unsaturated Ci-

C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, Cg, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆,

C₁₇, Cig, Ci9, C20 or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g., C C₂, C₃, C₄, C₅, C₆, C₇, Cg, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇,

Cig, Cig, C20 or C21-C30 hydrocarbyl). In some embodiments, R¹ is methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2- ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, isododecyl, methyldodecyl, ethyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n- eicosyl or n-tricosyl. In some embodiments, R¹ is an aromatic substituent. In some

embodiments, R¹ may comprise one or more heteroatoms, e.g. , oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, R¹ may comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy, a hydroxyl group, an amide, or an amine. In some embodiments,

R¹ is a polyol substituent, e.g., including 2, 3 or 4 hydroxyl groups. In some embodiments, R¹ is a saturated or unsaturated Cg-C3o fatty acid or a saturated or unsaturated Cg-C3o fatty alcohol, e.g., R is cetyl, oleyl or stearyl. In some embodiments, R is a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.

[0133] In some embodiments, R¹ is selected to increase the compatibility of the Diels-

Alder adduct with an oil, to increase solubility in water, or to increase solubility in electrolyte solutions. In some variations, the surfactant is nonionic, and R¹ comprises one or more hydroxyl groups such that the adduct is a primary alcohol, an amino group, a primary alcohol including an alkoxylate chain, an alkyl-capped alkoxylate, an amide, an ethanolamide, or one or more glucose groups. In some variations, the surfactant is anionic, and R¹ comprises a sulfate salt, a sulfonate salt, a carboxylate salt, or a phosphate salt. In some variations, the surfactant is cationic, and R¹ comprises a quaternary amine. In some variations, the surfactant is zwitterionic, and R¹ comprises an amine oxide.

[0134] In some embodiments, a Diels-Alder adduct between β-farnesene and acrylic acid or an acrylate ester results in a mixture of compounds having formulae (H-IA) and (HIB) in any relative amount may be used, e.g., a mixture comprising a ratio of formula (H-IA): formula (H- IB) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99: 1, or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H-IA): formula (H-IB) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight or by volume.

[0135] In some embodiments, a Diels-Alder adduct between β-farnesene and acrylic acid or an acrylate ester is hydrogenated, prior to use, to form a compound having formula (H-IC), or (H-ID) or an corner thereof, or a combination thereof:

2

[0136] where R may be H, or a linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted substituent, e.g. , C₁-C30. In some embodiments, R is an aliphatic C₁-C30 substituent. In some embodiments, R is a linear saturated or unsaturated Ci- C₃₀ hydrocarbyl group (e.g. , C C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cu, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, Ci₈, Ci9, C₂o or C₂i-C₃o hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g. , Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cu, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, Ci9, C₂o or C₂i-C₃o hydrocarbyl). In some embodiments, R is methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2- ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, isododecyl, methyldodecyl, ethyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-

2 2 eicosyl or n-tricosyl. In some embodiments, R is an aromatic group. In some embodiments, R may comprise one or more heteroatoms, e.g. , oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, R may comprise a carboxylic acid, an ester, a carbonyl, an ether, an polyalkoxylate, a hydroxyl group, an amide group, or an amine group. In some embodiments, R is a saturated or unsaturated C₈-C₃o fatty acid or a saturated or unsaturated C₈-C₃o fatty

2 2

alcohol, e.g., R is cetyl, oleyl or stearyl. In some embodiments, R is a C₁-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond. In some embodiments, R includes a polyol substituent, e.g., including 2, 3, or 4 hydroxy groups.

[0137] In some embodiments, R is selected to increase the compatibility of the Diels-

Alder adduct with an oil, to increase solubility in water, or to increase solubility in electrolyte solutions. In some variations, the surfactant is nonionic, and R is selected to that the adduct is a primary alcohol, an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, an ethanolamide, a glucoside, or a glucamide. In some variations, the surfactant is anionic, and R comprises a sulfate salt, a sulfonate salt, a carboxylate salt, or a phosphate salt. In some variations, the surfactant is cationic, and R comprises a quaternary amine. In some variations, the surfactant is zwitterionic, and R comprises an amine oxide.

[0138] In some embodiments, compounds of formula (H-IC) may be derived from compounds of formula (H-IA), and compounds of formula (H-ID) may be derived from compounds of formula (H-IB) by hydrogenation. In some embodiments, hydrogenation occurs

2

so that R is the same as R . In some embodiments, some degree of hydrogenation occurs in the 1 2 1

R group so that R is not the same as R . In some embodiments, compounds of formulae (H- IC) and (H-ID) are derived using additional chemical modification of a hydrogenated Diels- Alder adduct between β-farnesene and acrylic acid or an acrylate ester, so that R is not the same as R¹.

[0139] A mixture of compounds of formulae (H-IC) and (H-ID) in any relative amounts may be used in the applications described herein, e.g., a mixture comprising a ratio of formula (H-IC): formula (H-ID) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99:1, or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H-IC): formula (H-ID) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight or by volume.

[0140] A possible Diels-Alder adduct between a-farnesene and acrylic acid or an acrylate ester may have formula (H-IE), formula (H-IF), or an isomer thereof, or a mixture thereof:

where R¹ is as described in relation to formula (H-IA) and (H-IB).

[0141] In some embodiments, a Diels-Alder adduct between a-farnesene and acrylic acid or an acrylate ester results in a mixture of compounds having formulae (H-IE) and (H-IF) in any relative amount, e.g., a mixture comprising a ratio of formula (H-IE): formula (H-IF) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1 , or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H-IE): formula (H-IF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume. [0142] Compounds of formulae (H-IG) and (H-IH) may be obtained by hydrogenating formulae (H-IE) and (H-IF) or by any suitable route.

where R is as described in relation to formulae (H-IC) and (H-ID).

[0143] In certain embodiments, a compound having formula (H-IA), (H-IB), (H-IC), (H-

ID), (H-IE), (H-IF), (H-IG) and (H-IH) or a derivative thereof may have use as a solvent or surfactant.

(H-II) Dialkyl Maleate or Dialkyl Fumarate Dienophiles [0144] embodiments, a Diels-Alder adduct between β-farnesene and a dialkyl

maleate,

or maleic acid, in which the carboxylate groups are oriented as a cis-

isomer, or a dialkyl

or fumaric acid, in which the carboxylate groups are oriented as a trans-isomer, has utility in making surfactants as described herein, shown by formula (H-IIA):

where R 3 and R 3 ' are each independently H or a straight or branched chain, saturated or unsaturated, cyclic or acyclic, substituted or unsubstituted substituents or hydrocarbyl, e.g. C_\-

3 3' 3 3'

C30. In some embodiments, R and R are the same. In other embodiments, R and R are different. In some embodiments, each of R 3 and R 3' is independently a linear saturated or unsaturated C₁-C30 hydrocarbyl group {e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C_n, C₁₂, C₁₃, Ci4, Ci5, Ci6, Ci7, Ci8, C19, C20 or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g., C C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, C₁₅,

3 3 '

Ci6, Cn, Ci₈, Ci9, C₂o or C21-C30 hydrocarbyl). In some embodiments, each of R and R is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, isododecyl, methyldodecyl, ethyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n- heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl. In some embodiments, each of R

3 ' 3 3' and R is independently an aromatic group. In some embodiments, each of R and R may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or

3 3'

chloride. In some embodiments, each of R and R may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, a polyalkoxylate, a hydroxyl group, an amine, an amide, or

3 3 '

one or more glucose groups. In some embodiments, each of R and R may independently include a polyol substituent, e.g. , each of R 3 and R 3 ' may independently include 2, 3 or 4

3 3'

hydroxy groups. In some embodiments, each of R and R is independently a saturated or unsaturated C₈-C₃o fatty acid or a saturated or unsaturated C₈-C₃o fatty alcohol, e.g., each of R and R 3 ' may independently be cetyl, oleyl or stearyl. In some embodiments, each of R 3 and R 3' is independently a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond. It should be noted the carboxylate substituents on the adduct (H-IIA) have a 1,2-syn- orientation relative to each other originating from the cis- orientation of the carboxylate substituents if a maleate is used as a dienophile. If a 1,2-anti- orientation of the carboxylate substituents relative to each other on the adduct is desired, a dialkyl fumarate may be used as a dienophile instead of a dialkyl maleate.

3 3'

[0145] In some embodiments, each of R and R is independently selected to increase compatibility of the surfactant with an oil to be modified, or to increase solubility in water or in an electrolyte solution. In some variations, the surfactant is nonionic, and one or both of R and

3'

R may be selected so that the adduct comprises a primary alcohol (a monoalcohol or a diol), an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, an ethanolamide, or a glucoside. In one example of a nonionic surfactant, one of R is a carboxylic

3 3 '

acid and the other of R and R is a peracid. In some variations, the surfactant is anionic, and

3 3 '

one or both of R^J and R^J comprises a sulfate salt, a sulfonate salt, a carboxylate salt, or a

3 3 ' phosphate salt. In some variations, the surfactant is cationic, and one or both of R^J and R^J comprises a quaternary amine. In some variations, the surfactant is zwitterionic, and one or both

3 3 '

of R^J and R^J comprises an amine oxide. In some variations, the surfactant is zwitterionic, and

3 3' 3 3'

one of R and R is a carboxylic acid salt, and the other of R and R is an ammonium ion.

[0146] In some embodiments, a compound having formula (H-IIA) is obtained by derivatizing a Diels- Alder adduct between β-farnesene and a dienophile. For example, a compound having formula (H-IIA) may be obtained by making a Diels- Alder adduct between β- farnesene and maleic anhydride, hydrolysis of the farnesene-maleic anhydride adduct using known techniques to create a dicarboxylic acid, and esterifying the dicarboxylic acid using known techniques.

[0147] In some embodiments, it is desirable to create a diester Diels-Alder adduct in which the aliphatic tail originating from the β-farnesene is partially hydrogenated, or fully hydrogenated to form a hydrogenated adduct having formula (H-IIB):

where each of R⁴ and R⁴ is independently H or a straight or branched chain, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted substituents, e.g. C1-C30. In some embodiments, R⁴ and R⁴ are the same. In other embodiments, R⁴ and R⁴ are different. In some embodiments, each of R⁴ and R⁴ is independently a linear saturated or unsaturated C1-C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, Ci₈, Ci9, C₂o or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C9, Cio, Cn, C12, C13, Ci₄, C15, Ci₆, C₁₇, C₁₈, C19, C₂o or C21-C30 hydrocarbyl). In some embodiments, each of R⁴ and R⁴ is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, isododecyl, methyldodecyl, ethyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl. In some embodiments, one or both of R⁴ and R⁴ comprises an aromatic group (e.g., one or both of R⁴ and R⁴ may comprise a phenyl group or one or both of R⁴ and R^4' may be a benzyl group). In some embodiments, each of R⁴ and R⁴ may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, each of R⁴ and R⁴ may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, a polyalkoxylate, a hydroxyl group, an amide group, an amine group, or one or more glucose groups. In some embodiments, each of R⁴ and R⁴ may independently include a polyol substituent, e.g. , each of R⁴ and R⁴ may independently include 2, 3 or 4 hydroxyl groups. In some embodiments, each of R⁴ and/or R⁴ is independently a saturated or unsaturated C8-C30 fatty acid or a saturated or unsaturated C8-C30 fatty alcohol, e.g., each of R⁴ and R⁴ may independently be cetyl, oleyl or stearyl. In some embodiments, each of R⁴ and R⁴ is independently a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.

[0148] Compounds having formula (H-IIB) can be obtained by a variety of methods using Diels- Alder reactions. In some embodiments, compounds having formula (H-IIB) are derived by hydrogenating compounds having formula (H-IIA). In some embodiments, R and R³ are not affected by the hydrogenation so that R⁴ is the same as R³ and R⁴ is the same asR³ . In other embodiments, R³ and R³ are at least partially hydrogenated so that R⁴ and R⁴ are not

3 3' ·

the same as R^J and R^J . In some embodiments, compounds having formula (H-IIB) are derived by hydrogenating compounds having formula (H-IIB) with further chemical modification, e.g., to chemically modify R³ and/or R³ to form R⁴ and/or R⁴ respectively. In some embodiments, compounds having formula (H-IIB) are obtained by making a Diels- Alder adduct between β- farnesene and maleic anhydride, hydrogenating the adduct, and hydrolysis of the hydrogenated farnesene-maleic anhydride adduct using known techniques to create a dicarboxylic acid, and esterifying the dicarboxylic acid using known techniques. It should be noted that if (H-IIB) is derived by hydrogenating (H-IIA) made using a maleate dienophile, the carboxylate groups on (H-IIB) have a 1,2-syn- orientation relative to each other originating from cis- orientation of the carboxylate substituents on the maleate dienophile, and if (H-IIB) is derived by hydrogenating (H-IIA) made by using a fumarate dienophile, the carboxylate groups on (H-IIB) have a 1 ,2-anti orientation relative to each other originating from the trans- orientation of the carboxylate substituents on the fumarate dienophile.

[0149] In some embodiments, each of R⁴ and R⁴ is independently selected to increase compatibility of the surfactant with an oil to be modified, or to increase solubility in water or in an electrolyte solution. In some variations, the surfactant is nonionic, and one or both of R⁴ and R⁴ may be selected so that the adduct comprises a primary alcohol, an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, an ethanolamide, a glucoside, or a glucamide. In one example of a nonionic surfactant, one of R⁴ is a carboxylic acid and the other of R⁴ and R⁴ is a peracid. In some variations, the surfactant is anionic, and one or both of R⁴ and R^4' comprises a sulfate salt, a sulfonate salt, a carboxylate salt, or a phosphate salt. In some variations, the surfactant is cationic, and one or both of R⁴ and R⁴ comprises a quaternary amine. In some variations, the surfactant is zwitterionic, and one or both of R⁴ and R⁴ comprises an amine oxide. In some variations, the surfactant is zwitterionic, and one of R⁴ and R⁴ is a carboxylic acid salt, and the other of R⁴ and R⁴ is an ammonium ion.

[0150] In some embodiments, a Diels-Alder adduct between a-farnesene and a dialkyl

maleate,

or maleic acid, or a dialkyl fumarate or fumaric acid, has utility in the applications described herein, the adduct having formula (H-IIC):

3 3 '

where R and R are as described in relation to formula (H-IIA). It should be noted the carboxylate substituents on the adduct (H-IIC) have a 1 ,2-syn- orientation relative to each other originating from the cis- orientation of the carboxylate substituents if a maleate is used as a dienophile. If a 1,2-anti- orientation of the carboxylate substituents on the adduct is desired, a dialkyl fumarate may be used as a dienophile instead of a dialkyl maleate.

[0151] Compounds having formula (H-IID) may be made by hydrogenating compounds of formula (H-IIC), or by any suitable reduction reaction:

where R⁴ and R⁴ are as described in relation to formula (H-IIB). It should be noted that if (H- IID) is derived by hydrogenating (H-IIC) made using a maleate dienophile, the carboxylate groups on (H-IID) have a 1 ,2-syn- orientation relative to each other originating from cis- orientation of the carboxylate substituents on the maleate dienophile, and if (H-IID) is derived by hydrogenating (H-IIC) made by using a fumarate dienophile, the carboxylate groups on (H- IID) have a 1,2-anti- orientation relative to each other originating from the trans- orientation of the carboxylate substituents on the fumarate dienophile.

[0152] In certain embodiments, compounds of formula (H-IIA), (H-IIB), (H-IIC) and

(H-IID) or a derivative thereof may have use as solvents or surfactants.

(H-III) Maleic anhydride Dienophiles

[0153] In some embodiments, maleic anhydride is used as a dienophile in a Diels-Alder reaction with farnesene. A reaction product with β-farnesene is shown as compound (H-IIIA):

[0154] Compound (H-IIIA) can be hydrogenated to form Compound (H-IIIB).

[0155] A proposed Diels-Alder reaction product between a-farnesene and maleic anhydride is shown as Compound (H-IIIC):

[0156] Compound (H-IIIC) can be hydrogenated to form Compound (H-IIID).

[0157] In certain embodiments, the anhydride compounds (H-IIIA), (H-IIIB), (H-IIIC) and (H-IIID) or derivatives thereof may be used to make solvents or surfactants. In some embodiments, the anhydride compounds disclosed herein may be used as monomers in a polymerization reaction utilizing anhydrides as monomers. Such polymers may have utility as surfactants.

(H-IV) Diols

[0158] Additional compounds disclosed herein are compounds (H-IVA), (H-IVB), (H-

IVC) and (H-IVD):

[0159] Compounds (H-IVA), (H-IVB), (H-IVC) and (H-IVD) can be made by any suitable method. In some embodiments, a Diels-Alder adduct between β-farnesene and maleic acid, a dialkyl maleate, fumaric acid, or a dialkyl fumarate is reduced using known techniques (e.g., using lithium aluminum hydride) to form Compound (H-IVA). Compound (H-IVB) may be made by hydrogenating Compound (H-IVA), or alternatively by reducing Compound (H- IIIB) using known techniques. In some embodiments, a Diels-Alder adduct between a- farnesene and maleic acid, a dialkyl maleate, fumaric acid, or a dialkyl fumarate is reduced using known techniques (e.g., using lithium aluminum hydride) to form Compound (H-IVC).

Compound (H-IVD) may be made by hydrogenating Compound (H-IVC), or alternatively by reducing a compound having formula (H-IIID) using known techniques.

[0160] The diols of formulae (H-IVA), (H-IVB), (H-IVC) and (H-IVD) may be used in place of any diol as solvents and in surfactant formulations (e.g., in personal care formulations such as emollients, shampoos, cleansers, cosmetics, and the like; in emulsions; or in detergents and other cleaning formulations). The diols disclosed herein may be used as is as surfactants, or may be treated alkoxylated or otherwise derivatized to make a surfactant.

(H-V) Maleimide Dienophiles

[0161] Additional compounds disclosed herein are represented by formulae (H-V A), (H-

VB), (H-VC) and (H-VD):

where R⁵ and R⁵ may independently be H, a C1-C30 saturated or unsaturated, linear or branched chain, cyclic or acyclic, substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group. For example, each of R⁵ and R⁵ may independently be a linear saturated or unsaturated C1-C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C9, C₁₀, C11, C12, Co, Ci4, Ci5, Ci6, Ci7, C₁₈, Ci , C₂o or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, Ci5, Ci6, C₁₇, Ci8, Ci9, C₂o or C21-C30 hydrocarbyl). In some embodiments, each of R⁵ and R⁵ is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n- pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, isododecyl, methyldodecyl, ethyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n- heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl. In some embodiments, each of R⁵ and R⁵ is independently aromatic. In some embodiments, each of R⁵ and R⁵ may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, each of R⁵ and R⁵ may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or a hydroxyl group. In some embodiments, each of R⁵ and R⁵ is independently a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.

[0162] Compounds of formula (H-VA) may be obtained as a Diels- Alder reaction product between β-farnesene and a maleimide. Compounds of formula (H-VC) may be obtained as a Diels- Alder adduct between a-farnesene and a maleimide. In certain embodiments, the Diels-Alder adduct may be subsequently chemically modified to incorporate a desired functionality into the adduct. In some embodiments, a compound having formula (H-VB) may be derived by hydrogenating a compound having formula (H-VA). Similarly, a compound having formula (H-VD) may be derived by hydrogenating a compound having formula (H-VC). In some embodiments, a compound having formula (H-VB) is obtained by hydrogenating a compound having formula (H-VA), with additional chemical modification. In some

embodiments, a compound having formula (H-VD) is obtained by hydrogenating a compound having formula (H-VC), with additional chemical modification.

[0163] In certain embodiments, compounds of formulae (H-VA), (H-VB), (H-VC) and

(H-VD) or derivatives thereof have utility as solvents or surfactants.

(H-VI) Fumaronitrile Dienophiles

[0164] In some embodiments, fumaronitrile, CN _s undergoes a Diels-Alder reaction with β-farnesene or a-farnesene. The reaction product between β-farnesene and fumaronitrile is Compound (H-VIA) and the proposed reaction product between a-farnesene and fumaronitrile is Compound (H-VIB):

The cyano groups in the Diels-Alder adducts have a trans- orientation relative to each other originating from the trans orientation of the fumaronitrile.

[0165] In certain embodiments, compounds having formula (H-VIA) and (H-VIB) or derivatives thereof may be used to make solvents or surfactants. In some variations, compounds (H-VIA) and (H-VIB) are hydrogenated. The nitrile groups on compounds (H-VIA) and (H- VIB) may undergo hydrolysis under acid or base to form the dicarboxamide or dicarboxylic acid using known techniques. For example, compounds having structure (H-VIC) or (H-VID) may be derived from compound (H-VIA) using hydrolysis:

The trans- orientation of the substituents originating from the fumaronitrile is preserved for modified adducts such as (H-VIC) and (H-VID).

(H-VII) Aldehyde Dienophiles

[0166] In some embodiments, an unsaturated aldehyde is used as a dienophile in a Diels

Alder reaction with farnesene. Some unsaturated aldehydes have the formula

where R may be H, a linear or branched hydrocarbyl group or a halo substituent. In some embodim C₁-C30 alkyl . Non-limiting examples of unsaturated aldehydes include acrolein,

_s and crotonaldehyde, O . The reaction product between β- farnesene and acrolein may be Compound (H-VIIA) or (H-VIIB) or a mixture thereof in which Compound (H-VIIA) and Compound (H-VIIB) are present in any relative amounts, e.g., a mixture comprising a ratio of Compound (H-VIIA): Compound (H-VIIB) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H- VIIA):Compound (H-VIIB) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[0167] Proposed reaction products between a-farnesene and acrolein are illustrated by

Compounds (H-VIIC) and (H-VIID), where the reaction product may be (H-VIIC), (H-VIID), or a mixture thereof in which Compounds (H-VIIC) and (H-VIID) are present in any relative amounts, e.g., a ratio of Compound (H-VIIC) Compound (H-VIID) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight or by volume. In some embodiments, the ratio of Compound (H-VIIC): Compound (H-VIID) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[0168] Proposed reaction products between β-farnesene and crotonaldehyde are illustrated by Compounds (H-VIIE) and (H-VIIF), where the reaction product may be (H-VIIE), (H-VIIF), or a mixture thereof in which Compounds (H-VIIE) and (H-VIIF) are present in any relative amounts, e.g., a ratio of Compounds (H-VIIE): Compounds (H-VIIF) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99: 1, or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H- VIIE):Compound (H-VIIF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[0169] Proposed reaction products between a-farnesene and crotonaldehyde are illustrated by Compounds (H-VIIG) and (H-VIIH), where the reaction product may be

Compound (H-VIIG) or (H-VIIH), or a mixture thereof in which Compounds (H-VIIG) and (H- VIIH) are present in any relative amounts, e.g., a ratio of Compound (H-VIIG): Compound (H- VIIH) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H-VIIG) Compound (H-VIIH) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

(H-VIIH). [0170] In certain embodiments, compounds having formulae (H-VIIA), (H-VIIB), (H-

VIIC), (H-VIID), (H-VIIE), (H-VIIF), (H-VIIG), and (H-VIIH), or derivatives thereof may have utility as solvents or as surfactants. For example, compounds having formula (H-VIIA), (H- VIIB), (H-VIIC), (H-VIID), (H-VIIE), (H-VIIF), (H-VIIG), or (H-VIIH) may be hydrogenated, and alcohols derived from the aldehydes, e.g., as shown in Examples 3, 4, and 11 herein. As described herein and as illustrated in non- limiting Examples 3, 4, and 10-12, the alcohols may be ethoxylated to form a solvent or surfactant.

(H-VIII) Itaconate Dienophiles

[0171] In some embodiments, itaconic anhydride ,

_s itaconic acid,

or a dialkyl itaconate,

, is used as a dienophile in a Diels-Alder reaction with β- farnesene or a-farnesene, where R is any suitable hydrocarbyl group, e.g., a C₁-C30 hydrocarbyl group. Non-limiting examples of dialkyl itaconates that may be used include dimethyl itaconate, diethyl itaconate, di-n-butyl itaconate, di-sec-butyl itaconate, di-tert-butyl itaconate,

bis(cyclohexylmethyl) itaconate, dicyclohexyl itaconate, di-isopropyl methyl itaconate, di-n- pentyl itaconate, di-n-hexyl itaconate, di-n-heptyl itaconate, di-n-octyl itaconate, di-n-nonyl itaconate and di-n-decyl itaconate.

[0172] The reaction product between β-farnesene and itaconic acid or a dialkyl itaconate is illustrated by formulae (H-VIIIA) and (H-VIIIB) where R is H or any suitable hydrocarbyl group, e.g., a C₁-C30 hydrocarbyl group , where the reaction product may have formula (H- VIIIA) or (H-VIIIB), or a mixture thereof in which formula (H-VIIIA) and formula (H-VIIIB) are present in any relative amounts, e.g., a ratio of formula (H-VIIIA): formula (H-VIIIB) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99:1, or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H- VIIIA) formula (H-VIIIB) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

(H-VIIIA), (H-VIIIB).

[0173] The compounds of formulae (H-VIIIA) and (H-VIIIB) can be hydrogenated to form compounds of formulae (H-VIIIC) and (H-VIIID) respectively:

(H-VIIID).

[0174] It should be noted that compounds of formulae (H-VIIIC) and (H-VIIID) may undergo one or more subsequent chemical reactions so that R' is not the same as R. Such a reaction may be conducted prior to or following hydrogenation.

[0175] The reaction product between β-farnesene and itaconic anhydride is shown as

Compounds (H-VIIIE) and (H-VIIIF), where the reaction product may be Compound (H-VIIIE) or (H-VIIIF) or a mixture thereof in which Compound (H-VIIIE) and Compound (H-VIIIF) are present in any relative amounts, e.g., a ratio of Compound (H-VIIIE): Compound (H-VIIIF) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99:1, or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H-VIIIE): Compound (H-VIIIF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

(H-VIIIE), (H-VIIIF).

[0176] Compounds (H-VIIIE) and (H-VIIIF) may be hydrogenated to form Compounds

(H-VIIIG) and (H-VIIIH) respectively:

(H-VIIIH). [0177] It is contemplated that a-farnesene may undergo Diels- Alder reaction with itaconic anhydride, itaconic acid or a dialkyl itaconate. For example, possible reaction products between a-farnesene and itaconic anhydride are shown as Compounds (H- VIII J) and (H-VIIIK). The reaction product may be Compound (H-VIIIJ) or (H-VIIIK) or a mixture thereof, where Compounds (H-VIIIJ) and (H-VIIIK) are present in any relative amounts, e.g., a ratio

Compound (H-VIIIJ): Compound (H-VIIIK) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H-VIIIJ): Compound (H-VIIIK) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume. Compounds (H-VIIIL) and (H-VIIIM) may be obtained by hydrogenating Compounds (H-VIIIJ) and (H-VIIIK) respectively, or by any suitable route.

[0178] The anhydride compounds of formulae (H-VIIIA), (H-VIIIB), (H-VIIIC) and (H-

VIIID), and Compounds (H-VIIIE), (H-VIIIF), (H-VIIIG), (H-VIIIH), (H-VIIIJ), (H-VIIIK), (H- VIIIL) and (H-VIIIM) may be used in any application utilizing an anhydride. In certain embodiments, the anhydride compounds of formulae (H-VIIIA), (H-VIIIB), (H-VIIIC) and (H- VIIID), and Compounds (H-VIIIE), (H-VIIIF), (H-VIIIG), (H-VIIIH), (H-VIIIJ), (H-VIIIK), (H- VIIIL) and (H-VIIIM), and derivatives thereof may have utility as solvents or surfactants. R or R may be selected to increase compatibility of the surfactant with an oil to be modified, or to increase solubility in water or in an electrolyte solution. For example, the anhydride

functionality may be opened up using known techniques to form a diacid, which may be used as is as a surfactant, or further reacted to form a nonionic surfactant, a cationic surfactant, or a zwitterionic surfactant (e.g., an amine-oxide) as described herein.

(H-IX) Acetylene Dicarboxylic Acid and Acetylene Dicarboxylic Acid Ester Dienophiles

C0₂H

[0179] In some embodiments, acetylene dicarboxylic acid, ^H°2^C r- _s or acetylene

^CONH₂ ^C0₂R dicarboxamide, ^H2^{N OC} _s or an acetylene dicarboxylic acid ester, ^R°2^C _s where R can be any suitable hydrocarbyl group (e.g., C1-C30 hydrocarbyl), is used as a dienophile in a Diels- Alder reaction with farnesene.

[0180] A reaction product between β -farnesene and acetylene dicarboxylic acid is represented by Compounds (H-IXA) and (H-IXB), where the reaction product may be represented by Compound (H-IXA) or (H-IXB), or a mixture thereof, in which Compound (H- IXA) and Compound (H-IXB) are present in any relative amounts, e.g., a ratio of Compound (H- IXA):Compound (H-IXB) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H- IXA):Compound (H-IXB) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[0181] A reaction product between a-farnesene and acetylene dicarboxylic acid is represented by Compounds (H-IXC) and (H-IXD), where the reaction product may be represented by Compound (H-IXC) or (H-IXD), or a mixture thereof, in which Compound (H-

IXC) and Compound (H-IXD) are present in any relative amounts, e.g., a ratio of Compound (H-

IXC):Compound (H-IXD) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80,

30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H- IXC):Compound (H-IXD) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[0182] A reaction product between β-farnesene and an acetylene dicarboxylic acid ester is represented by formulae (H-IXE) and (H-IXF),where the reaction product may be represented by formula (H-IXE) or (H-IXF), or a mixture thereof, in which formula (H-IXE) and formula (H-IXF) are present in any relative amounts, e.g., a ratio of formula (H-IXE): formula (H-IXF) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H-IXE): formula (H-IXF) is from about

0.001 :99.999 to about 99.999:0.001 , from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

where each of R⁶ and R⁶ is independently H, a C₁-C30 saturated or unsaturated, linear or branched chain, cyclic or acyclic, substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group. For example each of R⁶ and R⁶ may independently be a linear saturated or unsaturated C₁-C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, Co, Ci₄, Ci₅, Ci₆, Ci₇, C₁₈, Ci , C₂o or C₂₁-C30 hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, Ci5, Ci6, C₁₇, Ci8, Ci9, C₂o or C21-C30 hydrocarbyl). In some embodiments, each of R⁵ and R⁵ is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n- pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, isododecyl, methyldodecyl, ethyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n- heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl. In some embodiments, each of R⁶ and R⁶ is independently aromatic (e.g., one or both of R⁶ and R⁶ may be phenyl or benzyl groups). In some embodiments, each of R⁶ and R⁶ may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen, or chloride. In some embodiments, each of R⁶ and R⁶ may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy, or a hydroxyl group. In some embodiments, each of R⁶ and R⁶ is independently a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.

[0183] A reaction product between a-farnesene and an acetylene dicarboxylic acid ester is represented by formulae (H-IXG) and (H-IXH), where the reaction product may be represented by formula (H-IXG) or (H-IXH) or a mixture thereof, in which formula (H-IXG) and formula (H-IXH) are present in any relative amounts, e.g., a ratio of formula (H- IXG):formula (H-IXH) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H-IXG): formula (H-IXH) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

where R⁶ and R⁶ are as described in relation to formulae (H-IXE) and (H-IXF).

[0184] Compounds (H-IXA), (H-IXB), (H-IXC) and (H-IXD) and Compounds of formulae (H-IXE), (H-IXF), (H-IXG), and (H-IXH) may be used in any surfactant application that utilizes an unsaturated carboxylic acid or unsaturated carboxylic acid ester. In some embodiments, Compounds (H-IXA) and (H-IXC), and Compounds of formulae (H-IXE) and (H- IXG) may be reacted with another conjugated terpene or conjugated diene. Compounds (H- IXA), (H-IXB), (H-IXC) and (H-IXD) and Compounds of formulae (H-IXE), (H-IXF), (H-IXG) and (H-IXH) and derivatives thereof may have utility solvents or surfactants.

(H-X) Acetylene diamide or Dicyanoacetylene Dienophiles

[0185] In some embodiments, an acetylene diamide or dicyanoacetylene is used as a dienophile with farnesene in a Diels-Alder reaction. A reaction product between an acetylene diamide and β-farnesene is represented by formulae (H-XA) and (H-XB), where the reaction product may have formula (H-XA) or (H-XB), or a mixture thereof , in which formulae (H-XA) and (H-XB) may be present in any relative amounts, a ratio of formula (H-XA): formula (H-XB) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, or 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H-XA): formula (H-XB) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[0186] A reaction product between an acetylene diamide and a-farnesene is represented by formulae (H-XC) and H- (XD), where the reaction product may be formula (H-XC) or (H- XD), or a mixture thereof, in which formulae (H-XC) and (H-XD) may be present in any relative amounts, e.g., a ratio of formula (H-XC): formula (H-XD) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, or 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H-XC): formula (H-XD) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[0187] A reaction product between dicyanoacetylene and β-farnesene is shown as

Compounds (H-XE) and (H-XF), where the reaction product may be Compound (H-XE) or (H- XF), or a mixture thereof, in which Compounds (H-XE) and (H-XF) may be present in any relative amounts, e.g., a ratio of Compound (H-XE): Compound (H-XF) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H-XE): Compound (H-XF) is from about 0.001 :99.999 to about 99.999:0.001 , from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[0188] A reaction product between dicyanoacetylene and a-farnesene is shown as

Compounds (H-XG) and (H-XH), where the reaction product may be Compound (H-XG) or (H- XH), or a mixture thereof, in which Compounds (H-XG) and (H-XH) may be present in any relative amounts, e.g., a ratio of Compound (H-XG): Compound (H-XH) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H-XG): Compound (H-XH) is from about 0.001 : 99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[0189] In some embodiments, dicyanoacetylene is derived from acetylene dicarboxylic acid, following by treatment with ammoniolysis, followed by dehydration with P₂O₅ or the like. In some embodiments, dicyanoacetylene is derived from acetylene diamide, followed by dehydration with P₂O₅ or the like. In some embodiments, a Diels-Alder adduct between β- farnesene and acetylene dicarboxylic acid or acetylene diamide is dehydrated to make

Compound (H-XE) or (H-XF) or a mixture thereof, or a Diels-Alder adduct between a- farnesene and acetylene dicarboxylic acid or acetylene diamide is dehydrated to make

Compound (H-XG) or (H-XH) or a mixture thereof.

[0190] Compounds of formulae (H-XA), (H-XB), (H-XC) and (H-XD), and Compounds

(H-XE), (H-XF), (H-XG) and (H-XH) may be used in any application that utilizes an

unsaturated diamide or saturated dicyanoacetylene. In some embodiments, compounds of formula (H-XA) and (H-XC), and Compounds (H-XE) and (H-XG) may be reacted with another conjugated terpene or conjugated diene (e.g., 1 ,3-butadiene or a substituted 1 ,3 -butadiene). Compounds of formula (H-XA), (H-XB), (H-XC) and (H-XD), and Compounds (H-XE), (H- XF), (H-XG) and (H-XH) and derivatives thereof may have utility as surfactants.

(H-XI) Quinone Dienophiles

[0191] In some embodiments, a benzoquinone or a naphthoquinone is used as a dienophile. For example, Compound (H-XIA), (H-XIB) or (H-XIC) may be made as a Diels- Alder adduct between β-farnesene and 1 ,4-benzoquinone. Compounds (H-XIA), (H-XIB) and (H-XIC) may be hydrogenated to form compounds (H-XID), (H-XIE) and (H-XIF) respectively.

[0192] In some embodiments, only one of Compounds (H-XIA), (H-XIB) and (H-XIC) is produced during a Diels-Alder reaction. For example, the reaction conditions may be slowed or otherwise controlled to produce only Compound (H-XIA). In some embodiments, the reaction conditions may favor formation of a mixture of Compounds (H-XIB) and (H-XIC) in which Compounds (H-XIB) and (H-XIC) are present in any relative amounts, e.g., a ratio of Compound (H-XIB): Compound (H-XIC) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, or 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H-XIB) Compound (H-XIC) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume. In some embodiments, all three of compounds (H-XIA), (H- XIB) and (H-XIC) are present.

[0193] In some embodiments, Compound (H-XIA) may be oxidized to form a benzoquinone having structure (Η-ΧΙΑ'):

[0194] In some embodiments, Compounds (H-XIB) and/or (H-XIC) may be oxidized to form a benzoquinone having structures (Η-ΧΙΒ') and (H-XIC), respectively:

[0195] In some embodiments, Compounds (H-XIB) and/or (H-XIC) may be oxidized to form an anthraquinone having structures (H-XIB") and (H-XIC") respectively:

[0196] When 1 ,2-benzoquinone is used as the dienophile in a reaction with β-farnesene, one or more of Compounds (H-XID), (H-XIE), (H-XIF), (H-XIG) and (H-XIH) may result:

[0198] a-Farnesene may also react with 1,4-benzoquinone or 1 ,2-benzoquinone in a

Diels-Alder reaction. Possible reaction products with a-farnesene and 1,4-benzoquinone are Compounds (H-XIK)-(H-XIM):

[0199] Possible reaction products between a-farnesene and 1 ,2-benzoquinone are

Compounds (H-XIN)-( H-XIR):

[0200] A possible reaction product between a-farnesene and 1 ,4-naphthoquinone is

Compound (H-XIS):

[0201] It should be pointed out that aliphatic portions of any of Compounds (H-XIA)-

(H-XIS) may be completely or partially hydrogenated prior to use. Compounds of formulae (H- XIA)-( H-XIS) may be used in any application that utilizes ketones or quinones. In some embodiments, Compounds (H-XIA)-(H-XIS) and derivatives thereof may have utility as surfactants.

(H-XII) Oxidation of Diels-Alder Adducts

[0202] As described above, one or more unsaturated bonds of a conjugated hydrocarbon terpene may be oxidized (e.g., epoxidized). Non-limiting examples of mono-epoxides, di- epoxides, tri-epoxides, and tetra-epoxides derived from β-farnesene are Compounds (15a), (15b), (16), (17) and (18) as shown below:

[0203] In certain embodiments, one or more unsaturated bonds originating from the conjugated terpene in a Diels-Alder adduct is oxidized (e.g., epoxidized). For example, an epoxidized Diels-Alder adduct having any of structures (H-XIIA)-(H-XIIF) may be formed. Following the epoxidation, one or more remaining double bonds of adducts (H-XIIA)-(H-XIIE) may be hydrogenated to the corresponding Compounds (H-XII A')-(H-XIIE') as shown below:

where each of R and R' independently represents H or any C1-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted alkyl group, and R and R' may be the same or different. In some embodiments, each of R and R' independently represents a C₁-C₄ linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or t-butyl. In some embodiments, each of R and R' independently represent n-pentyl, isopentyl, n-hexyl, 2- ethylhexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n- hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl. In some

embodiments, each of R and R' is independently substituted with one or more heteroatoms, e.g., oxygen, nitrogen, or chlorine. In one embodiment, each of R and R' is independently methyl. In certain variations, a polyol may be derived from epoxidized Diels-Alder derivatives using known techniques.

[0204] It should be understood that any suitable Diels-Alder adduct described herein may be oxidized in a similar fashion. Diels-Alder adducts in which unsaturated bonds on the hydrocarbon tail or cyclohexene ring that have been oxidized to form epoxy groups or hydroxyl groups, or derivatives thereof may have utility as solvents or surfactants. [0205] As described above, one or more unsaturated bonds (e.g., in the aliphatic tail originating from the conjugated hydrocarbon terpene) may be halogenated (e.g., chlorinated). Halogenated Diels-Alder adducts or derivatives thereof may have utility as surfactants or solvents.

J) VARIATIONS OF SURFACTANTS

[0206] The Diels-Alder adduct surfactants as described herein may be nonionic, anionic, cationic, or zwitterionic (e.g., amine-oxides).

[0207] Advantageously, any of the surfactants comprising or derived from the Diels-

Alder adducts described herein may be made from conjugated terpenes and/or dienophiles that have been derived from renewable carbon sources. As used herein, a "renewable carbon" source refers to a carbon source that is made from modern carbon that can be regenerated within a several months, years or decades rather than a carbon source derived from fossil fuels (e.g., petroleum) that takes typically a million years or more to regenerate. The terms "renewable carbon" "biobased carbon" are used interchangeably herein. "Atmospheric carbon" refers to carbon atoms from carbon dioxide molecules that have been free in earth's atmosphere recently, in the most recent few decades.

[0208] Renewable carbon content can be measured using any suitable method. For example, renewable carbon content can be measured according to ASTM D6866-11 , "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis," published by ASTM International, which is incorporated herein by reference in its entirety. Some carbon in atmospheric carbon dioxide is the radioactive ¹⁴C isotope, having a half- life of about 5730 years. Atmospheric carbon dioxide is utilized by plants to make organic molecules. The atmospheric ¹⁴C becomes part of biologically produced substances. As the biologically produced organic molecules degrade to produce carbon dioxide into the atmosphere, no net increase of carbon in the atmosphere is produced as a result, which may control or diminish undesired climate effects that may result when molecules produced from fossil fuels degrade to produce carbon dioxide to increase carbon in the atmosphere.

[0209] Isotope fractionation occurs during physical processes and chemical reactions, and is accounted for during radiocarbon measurements. Isotope fractionation results in enrichment of one isotope over another isotope. Exemplary processes that can affect isotope fractionation include diffusion (e.g., thermal diffusion), evaporation, and condensation. In some chemical reactions, certain isotopes may exhibit different equilibrium behaviors than others. In some chemical reactions, kinetic effects may affect isotope ratios. In the carbon cycle of plants, isotope fractionation occurs. During photosynthesis, the relative amounts of different carbon isotopes that are consumed are ¹²C>¹³C>¹⁴C, due to slower processing of heavier isotopes. Plants species exhibit different isotope fractionation due to isotopic discrimination of photosynthetic enzymes and diffusion effects of their stomata. For example C3 plants exhibit different isotope fractionation than C₄ plants. The international reference standard for isotope

13 12

fractionation between C and C is PDB (Pee Dee Belemnite standard) or VPDB (Vienna Pee Dee Belemnite standard, replacement for depleted PDB standard). For a given sample, isotope

13

fractionation can be expressed as δ C (per mil) = {[R(sample)/R(VPDB standard)]-l }xl000 %o, where R(sample)=¹³C/¹²C and R(VPDB standard)=¹³C/¹²C for the VPDB standard. Instead

13 12 13 13 12

of a CI C ratio, δ C is the relative change of the CI C ratio for a given sample from that of

13 the VPDB standard. Carbon isotopic ratios are reported on a scale defined by adopting a δ C value of +0.00195 for NBS-19 limestone (RM 8544) relative to VPDB. "New IUPAC guidelines for the reporting of stable hydrogen, carbon, and oxygen isotope-ratio data," Letter to the Editor, J. Res. Natl. Stand. Technol. 100, 285 (1995). Most naturally occurring materials

13 13 0 exhibit negative δ values. In general, for atmospheric C0₂ δ ranges between -1 1 to -6 /₀₀,

13 0 13

for C3 plants, δ C varies between -22 and -32 /₀₀₎ and for C₄ plants δ C varies between -8 to - 18 %ο· The ¹⁴C fractionation factor can be approximated as the square of the ¹³C fractionation factor. See, e.g., M. Stuiver and S.W. Robinson, Earth and Planetary Science Letters, vol. 23, 87-90.

[0210] ¹⁴C content of a sample can be measured using any suitable method. For example, ¹⁴C content can be measured using Accelerator Mass Spectrometry (AMS), Isotope Ratio Mass Spectrometry (IRMS), Liquid Scintillation Counting (LSC), or a combination of two or more of the foregoing, using known instruments. Activity refers to the number of decays measured per unit time and per unit mass units. To compare activity of a sample with that of a known reference material, isotope fractionation effects can be normalized. If an activity of a sample is measured to be As, the sample activity normalized to the reference is ASN and can be expressed as: A_SN=A_s {[(¹³C/¹²C)reference]/[(¹³C/¹²C)sample]}².

[0211] Radiocarbon measurements are performed relative to a standard having known radioactivitiy. SRM 4990B is an oxalic acid dehydrate Standard Reference Material provided by the U.S. National Bureau of Standards (now National Institute of Standards and Technology, NIST) in the late 1950s having 6¹³C=-19 %₀ (PDB). SRM 4990B has been depleted so another

13 standard is used, such as SRM 4990C, a second oxalic acid standard from NIST having δ C=-

17.8 %o (VPDB). Modern carbon, referenced to AD 1950, is 0.95 times ¹⁴C concentration of SRM 4990B, normalized to 5^1JC=-19 ₀₀ (PDB). The factor 0.95 is used to correct the value to 1950 because by the late 1950s, ¹⁴C in the atmosphere had artificially risen about 5% above natural values due to testing of thermonuclear weapons. Fraction of modern (f_M) refers to a radiocarbon measured compared to modern carbon, referenced to AD 1950. Modern carbon as defined above has

· For current living plant material not more than a few years old (such as corn), ΪΜ is approximately 1.1. Percent modern carbon (pMC) is

x 100%. The AD 1950 standard had 100 pMC. Fresh plant material may exhibit a pMC value of about 107.5.

Biobased carbon content is determined by setting 100%> biobased carbon equal to the pMC value of freshly grown plant material (such as corn), and pMC value of zero corresponds to a sample in which all of the carbon is derived from fossil fuel (e.g., petroleum). A sample containing both modern carbon and carbon from fossil fuels will exhibit a biobased carbon content between 0 and 100%. In some cases, a sample that is more than several years old but containing all biobased carbon (such as wood from a mature tree trunk) will exhibit a pMC value to yield a biobased carbon content > 100%.

[0212] Renewable carbon content or biobased carbon content as used herein refers to fraction or percent modern carbon determined by measuring ¹⁴C content, e.g., by any of Method A, Method B, or Method C as described in ASTM D6866-11 "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis." Counts from ¹⁴C in a sample can be compared directly or through secondary standards to SRM 4990C. A measurement of 0% ¹⁴C relative to the appropriate standard indicates carbon originating entirely from fossils (e.g., petroleum based). A measurement of 100% ¹⁴C indicates carbon originating entirely from modern sources. A measurement of >100% ¹⁴C indicates the source of carbon has an age of more than several years.

[0213] In some variations, at least about 25%, at least about 30%, at least about 40%, at least about 50%>, at least about 60%>, at least about 70%>, at least about 80%>, at least about 90%>, or about 100% of the carbon atoms in the Diels-Alder adducts or derivatives thereof originate from renewable carbon sources. In some variations, the Diels-Alder adducts or derivatives have a 5¹³C of from about -11 to about -6 %₀, from about -15 to about -10 %₀, from about -22 to about -15 %o, from about -22 to about -32 %₀, from -8 to about -18 %₀, from about -14 to about -12 %o, or from about -13 to about -11 %₀. In some variations, the Diels-Alder adducts or derivatives have a ΪΜ greater than about 0.3, greater than about 0.4, greater than about 0.5, greater than about 0.6, greater than 0.7, greater than about 0.8, greater than about 0.9, or greater than about 1.0. In some variations, the Diels-Alder derivatives have a f_M of about 1.0 to about 1.05, about 1.0 to about 1.1 , or about 1.1 to about 1.2. In some variations, the Diels-Alder

13 0

derivatives have a δ C from about -15 to about -10 /₀₀ and a ΪΜ greater than about 0.5, greater than about 0.7, or greater than about 1.0. In some variations, the Diels-Alder derivatives have a

13 0

δ C from about -8 to about -18 /₀₀ and a ΪΜ greater than about 0.5, greater than about 0.7, or greater than about 1.0. In some variations, the conjugated hydrocarbon terpene (e.g., myrcene, β-farnesene, or a-farnesene) is made by genetically modified microorganisms using renewable carbon sources such as a sugar (e.g., sugar cane). In some variations, a dienophile is at least partially derived from renewable carbon sources. For example, a dienophile may be derived from ethanol derived from plant sources, e.g., a dienophile may be derived from renewable ethylene that is derived from renewable ethanol. In some variations, one or more chemicals used to modify the Diels-Alder adducts described herein may be at least partially derived from renewable carbon sources. For example, renewable alcohols, renewable diols (e.g., 1 ,4-butane diol), renewable glycols (e.g., ethylene glycol or propylene glycol) may be used to derivatize a Diels-Alder adduct as described herein. The renewable carbon content of a Diels-Alder adduct or its derivatives may be measured using any suitable method, e.g., using radiocarbon analysis as described herein.

[0214] Advantageously, the properties of a Diels-Alder surfactant formed from a conjugated terpene and a dienophile may be tuned, adjusted or modified to accomplish any one of or any combination of two or more of the following: i) modify hydrophobicity and/or hydophilicity of a portion or the whole of the molecule; ii) modify compatibility with a desired oil; iii) improve solubility in water (e.g., hard water or cold water) in use; iv) improve solubility in electrolytes (e.g., builders); v) provide a reactive site by which the adduct may react with another component of a composition incorporating the adduct; vi) increase thermal stability; vii) undergo a reverse Diels-Alder reaction to produce desired species; viii) modify molecular weight; ix) modify viscosity, crystallinity, or volatility at processing temperatures and/or at use temperatures; x) modify migration or leaching behavior in operation; xi) enable the surfactant to be suitable for use in food grade applications; xii) enable the surfactant to be suitable for use in medical applications; xii) modify surface tension or interfacial tension; xiii) provide a site for making an anion or cation; xiv) modify critical micelle concentration; xv) modify ability to form a stable emulsion with a specified oil; xvi) provide antistatic properties; or xvii) provide antimicrobial properties. Such tuning may be accomplished via choice of conjugated terpene and dienophile combination and/or by post-reaction chemical modifications as described herein or otherwise known. [0215] In certain embodiments, the surfactants described herein have a structure X_HC_T-

A_DA-Y_DP, in which X_HC_T represents one or more hydrophobic tails originating from one or more conjugated hydrocarbon terpenes reacted with a dienophile, Y_Dp represents one or more hydrophilic heads originating from one or more dienophiles, and A_DA comprises one or more cyclic groups (e.g., a 6-membered ring) resulting from the Diels-Alder reaction between the dienophile and the one or more conjugated hydrocarbon terpenes. A Diels-Alder surfactant may have a single hydrophobic tail and a single hydrophilic head in certain embodiments. In some embodiments, a surfactant may have a single hydrophobic tail and two hydrophilic heads so as to have structure ^{^}^_W .

[0216] In some embodiments, a surfactant has two hydrophobic tails and a single hydrophilic head. For example, two conjugated hydrocarbon terpenes (which may be the same or different) undergo a Diels-Alder reaction with one dienophile so that the surfactants may have

a structure ^x ₂ , where X_HC_TI refers to a first conjugated terpene and A_DAI refers to a cyclic group resulting from the Diels-Alder reaction between the first conjugated terpene and the dienophile, and X_HC_T2 refers to a second conjugated terpene and A_DA2 refers to a cyclic group resulting from the Diels-Alder reaction between the second conjugated terpene and the dienophile. In other variations, a surfactant having two hydrophobic tails and a single

hydrophilic head has a structure

_s which may result from a Diels-Alder reaction with a hydrocarbon terpene having an internal conjugated diene (e.g., isodehydrosqualene, isosqualane precursor I, or isosqualane precursor II) that reacts with a dienophile.

[0217] In some variations, a Diels-Alder surfactant has two hydrophobic tails and two

hydrophobic heads. For example, such a surfactant may have structure

[0218] X_HC_T and/or Y_DP may be selected or chemically modified to make the Diels-Alder adduct suitable for use in certain surfactant applications. X_HC_T (which encompasses X_HC_TI, where i=l, 2, or an even higher number) represents one or more hydrophobic tails originating from one or more hydrocarbon terpenes. YDP (which encompasses YD_PI, where i=l , 2, or an even higher number) represents one or more hydrophilic heads originating or derived from one or more dienophiles. In some variations, XHCT is a C10-C30 (e.g., C10-C15, or C10-C20, C10-C25, or C10-C30) hydrocarbon tail comprising one or more methyl branches having formula (X), (XI), (XIII), or (XIV) as shown herein. In some variations, XHCT comprises no heteroatoms. In some variations, XHCT comprises oxygen atoms, e.g., having formula (XII) or an oxidized version thereof. YDP may contain heteroatoms such as O, S, P or N. YDP may be neutral to make a nonionic surfactant, may comprise an anion to make an anionic surfactant, may comprise a cation to make a cationic surfactant, or may comprise a zwitterion to make a zwitterionic surfactant.

[0219] The hydrophobicity of XHCT may be tuned or modified in a variety of ways.

XHCT in general includes methyl substituents originating from the conjugated terpene. In some embodiments, XHCT is an unsaturated hydrocarbon chain, in other embodiments, XHCT is a saturated hydrocarbon chain, in some embodiments XHCT includes one or more nonionic oxygen groups (e.g., epoxy, hydroxy) or halogen atoms. Hydrophobicity of XHCT may be decreased by using a shorter chain conjugated terpene and/or oxidizing or halogenating one or more of the unsaturated carbon carbon bonds of XHCT-

[0220] Hydrophilicity of YDP may be tuned or modified in a variety of ways. In one example, a dienophile may be selected to vary the number of polar substituents on the Diels- Alder surfactant. For example, in some situations a dienophile may be selected that enables only one polar substituent to the cyclic group formed by the Diels-Alder reaction. In other, a dienophile may be selected that enables more than one (e.g., two) polar substituents to the cyclic group formed by the Diels-Alder reaction, e.g., a dienophile that is an anhydride, a diacid, a diester, or a di-cyano may be selected. In some embodiments, a Diels-Alder adduct is alkoxylated (any number of ethylene oxide or propylene oxide segments are incorporated into the adduct) to tune hydrophilicity.

[0221] XHCT and/or Y_Dp may be selected or chemically modified to accomplish any one of or any combination of the following: i) modify hydrophobicity and/or hydophilicity of a portion or the whole of the molecule; ii) modify compatibility with a desired oil, or other solvent; iii) improve solubility in water (e.g., hard water or cold water) in use; iv) improve solubility in electrolytes; v) provide a reactive site by which the adduct may react with another component of a composition incorporating the adduct; vi) undergo a reverse Diels-Alder reaction to produce desired species; vii) inhibit chemical reaction with other components that may be present in a composition; viii) increase thermal stability; ix) increase light stability; x) modify molecular weight; xi) modify volatility; xii) modify viscosity, crystallinity, or volatility at processing temperatures and/or at use temperatures; xiii) modify migration or leaching behavior in operation; xiv) enable the surfactant to be suitable for use in food grade applications; xv) enable the surfactant to be suitable for use in medical applications; xvi) modify surface tension or interfacial tension; xvii) provide a site for making an anion or cation; xviii) modify critical micelle concentration; xix) modify ability to form a stable emulsion with a specified oil; xx) provide antistatic properties; xxi) modify color, UV absorption and/or color stability; xxii) provide antimicrobial properties; xxiii) provide a desired stereoisomer or modify optical activity. Such tuning may be accomplished via choice of conjugated terpene and dienophile combination and/or by post-reaction chemical modifications as described herein or otherwise known.

[0222] In some variations, a surfactant has structure (Bl), where one of or both of RB and RB represent hydrophobic tails originating from one or more hydrocarbon terpenes, and

1 2

QB and QB represent one or two hydrophilic heads originating from one or more dienophiles.

[0223] In some variations, a Diels-Alder surfactant molecule has structure (Bl) with a single hydrophobic tail originating from a hydrocarbon terpene and a single hydrophilic head originating from the dienophile. For example, in the instances in which carbon-carbon double bonds have been saturated, such a surfactant molecule may be represented by formula (J la), (Jib) or a mixture thereof:

where RB¹, RB³ and RB⁴ are as described in connection with formula (Bl) herein, XHCT⁼RB² which represents the hydrophobic tail originating from the hydrocarbon terpene,^.!¹ is H or a

C1-C30 hydrocarbyl group, and Y_Dp represents the residual of any suitable dienophile as described herein or otherwise known following the Diels-Alder reaction. Non-limiting examples of combinations of RB¹, RB², RB³ and RB⁴ are provided in Table 1 herein, and non- limiting examples of Diels-Alder adducts are provided in Table 2 herein. In some cases, X_HC_T has formula (XI) with n=l,2,3, or 4 or formula (XIII) with m=l,2,3, or 4. In some variations, each of RB¹, RB³, RB⁴ and RJ¹ are H. In some variations, Y_DP renders the surfactant nonionic, and comprises -CH₂OH, a carboxylic acid, a carboxylic acid ester group (e.g., a methyl ester or an ethyl ester), an alkoxylated alcohol comprising about 1 to about 200 alkoxylate groups (e.g., 5, 9, 10, 15, 20, 50, 100, 150, or 200 alkoxylate groups), a carboxamide group, a glucoside, an ethanolamide or a glucamide. In some variations, Y_DP renders the surfactant cationic, e.g., comprises a quaternary ammonium ion. In some variations, Y_DP renders the surfactant anionic, e.g., comprises a carboxylate salt, a sulfonate, a sulfate, or a phosphate. In some variations, Y_DP comprises a zwitterionic moiety (e.g., an amine -oxide).

[0224] In some variations, a Diels-Alder surfactant molecule has structure (Bl) with a single hydrophobic tail and two hydrophilic heads. For example, in the instances in which carbon-carbon double bonds have been saturated, such a surfactant molecule may be represented by formula (J2). Structure (J2) corresponds to structure (Bl) with RB =X_HC_T which represents the hydrophobic tail originating from the hydrocarbon terpene.

where RB¹, RB³ and RB⁴ are as described in connection with formula (Bl) herein, X_HC_T ⁼RB² which represents the hydrophobic tail originating from the hydrocarbon terpene, and Y_DPI and Y_DP2 represent the residual of any suitable dienophile as described herein or otherwise known following the Diels-Alder reaction. Non-limiting examples of combinations of RB 1 , RB2 , RB 3 and RB⁴ are provided in Table 1 herein, and non- limiting examples of Diels-Alder adducts are provided in Table 2 herein. In some cases, Xncr has formula (XI) with n= 1,2,3, or 4 or formula (XIII) with m=l,2,3, or 4. In some variations, each of RB¹, RB³, RB⁴ are H. In some variations, Y_DPI and Y_DP2 render the surfactant nonionic, and one of or both of Y_DPI and Y_DP2 comprises - CH₂OH, a carboxylic acid, a carboxylic acid ester group (e.g., a methyl ester or an ethyl ester), an alkoxylated alcohol comprising about 1 to about 200 alkoxylate groups (e.g., 5, 9, 10, 15, 20, 50, 100, 150, or 200), a carboxamide group, a glucoside, an amide alkanolamine or a glucamide. In some variations, one or both of Y_DPI and Y_DP2 render the surfactant cationic, e.g., comprises a quaternary ammonium ion. In some variations, one of or both of Y_DPI and Y_DP2 renders the surfactant anionic, e.g., comprises a carboxylate salt, a sulfonate, a sulfate, or a phosphate. In some variations, at least one of Y_DP and Y_DP2 comprises an amine-oxide moiety.

[0225] In some variations, a surfactant molecule has structure (Bl) and comprises two hydrophobic tails and a single hydrophilic head. For example, in those instances in which unsaturated carbon-carbon bonds have been saturated, such a surfactant has structure (J3a), (J3b), or comprises a mixture of structures (J3a) and (J3b), or has structure (J4):

where RB 1 and RB3 are as described in connection with formula (Bl) herein, 2

X_HC_TI⁼RB and X_HC_T2=RB⁴ which represents the hydrophobic tails originating from one or more hydrocarbon terpenes. RJ is H or a C1-C30 hydrocarbyl group, and Y_DP represents the residual of any suitable dienophile as described herein or otherwise known following the Diels-Alder reaction. Non- limiting examples of combinations of RB¹, RB², RB³ and RB⁴ are provided in Table 1 herein, and non-limiting examples of Diels-Alder adducts are provided in Table 2 herein. In some cases, X_HC_TI and X_HC_T2 have formula (XI) with n= 1,2,3, or 4 or formula (XIII) with

1 3 1

m=l,2,3, or 4. In some variations, each of RB , RB and RJ are H. In some variations, Y_DP renders the surfactant nonionic, and comprises -CH₂OH, a carboxylic acid, a carboxylic acid ester group (e.g., a methyl ester or an ethyl ester), an alkoxylated alcohol comprising abou t 1 to about 200 alkoxylate groups (e.g., 5, 9, 10, 15, 20, 50, 100, 150, or 200 alkoxylate groups), a carboxamide group, a glucoside, an ethanolamide, or a glucamide. In some variations, Y_DP renders the surfactant cationic, e.g., comprises a quaternary ammonium ion. In some variations, Y_DP renders the surfactant anionic, e.g., comprises a carboxylate salt, a sulfonate, a sulfate, or a phosphate. In some variations, Y_DP comprises a zwitterion (e.g., an amine-oxide moiety).

[0226] In some variations, a Diels-Alder surfactant molecule has structure (Bl) with two hydrophobic tails and two hydrophilic heads. For example, in the instances in which carbon- carbon double bonds have been saturated, such a surfactant molecule may be represented by formula (J5):

where RB¹, RB³ and RB⁴ are as described in connection with formula (Bl) herein, X_HC_T ⁼RB² which represents the hydrophobic tail originating from the hydrocarbon terpene, and Y_DPI and Y_DP2 represent the residual of any suitable dienophile as described herein or otherwise known following the Diels-Alder reaction. Non-limiting examples of combinations of RB 1 , RB2 , RB 3 and RB⁴ are provided in Table 1 herein, and non- limiting examples of Diels-Alder adducts are provided in Table 2 herein. In some cases, X_Hcr has formula (XI) with n= 1 ,2,3, or 4 or formula (XIV) with m=l,2,3, or 4. In some variations, each of RB¹, RB³, and RB⁴ are H. In some variations, Y_DPI and Y_DP2 render the surfactant nonionic, and one of or both of Y_DPI and Y_DP2 comprise -CH₂OH, a carboxylic acid, a carboxylic acid ester group (e.g., a methyl ester or an ethyl ester), an alkoxylated alcohol comprising about 1 to about 200 alkoxylate groups (e.g., 5, 9, 10, 15, 20, 50, 100, 150, or 200 alkoxylate groups), a carboxamide group, a glucoside, an ethanolamide, or a glucamide. In some variations, one or both of Y_DPI and Y_DP2 render the surfactant cationic, e.g., comprises a quaternary ammonium ion. In some variations, one of or both of Y_DPI and Y_DP2 renders the surfactant anionic, e.g., comprises a carboxylate salt, a sulfonate, a sulfate, or a phosphate. In some variations, at least one of Y_Dp and Y_Dp₂ comprises a zwitterion (e.g., an amine-oxide moiety or a betaine).

[0227] In some variations, a surfactant molecule has formula (Bl) with two hydrophobic tails and two hydrophilic heads has formula (J6):

Non- limiting examples of combinations of RB¹, RB², RB³ and RB⁴ are provided in Table 1 herein, and non-limiting examples of Diels-Alder adducts are provided in Table 2 herein. In some cases, X_HC_TI and X_HC_T2 have formula (XI) with n= 1,2,3, or 4 or formula (XIV) with m=l,2,3, or 4. In some variations, each of RB 1 and RB 3 are H. In some variations, Y_DPI and Y_DP2 render the surfactant nonionic, and one of or both of Y_DPI and Y_DP2 comprise -CH₂OH, a carboxylic acid, a carboxylic acid ester group (e.g., a methyl ester or an ethyl ester), an alkoxylated alcohol comprising about 1 to about 200 alkoxylate groups (e.g., 5, 9, 10, 15, 20, 50, 100, 150, or 200 alkoxylate groups), a carboxamide group, a glucoside, an ethanolamide, or a glucamide. In some variations, one or both of Y_DPI and Y_DP2 render the surfactant cationic, e.g., comprises a quaternary ammonium ion. In some variations, one of or both of Y_DPI and Y_DP2 renders the surfactant anionic, e.g., comprises a carboxylate salt, a sulfonate, a sulfate, or a phosphate. In some variations, at least one of Y_DP and Y_DP2 comprises a zwitterion (e.g., an amine-oxide moiety).

[0228] In some variations, a solubility parameter may be calculated or measured for the

Diels-Alder surfactants as described herein to determine their effectiveness in a particular application, e.g., in an emulsion, or as a solvent. Any suitable solubility parameter may be calculated or measured, e.g., a Hansen solubility parameter. Hansen Solubility Parameters (HSP) have been used to correlate solubility of solvents and solutes. The first principle from HSP is that each chemical can be characterized by three parameters, 5D which is the Dispersion component that represents the polarizability (available electrons) of a molecule, δΡ which is the Polar component that correlates well with dipole moments and δΗ which is the hydrogen- bonding component which correlates well with, for example, -OH groups in a molecule. The second principle is that "like dissolves like" and that for HSP the definition of "like" is the "Distance" between molecules 1 and 2 which is defined as:

Distance = Sqrt(4(5Di-5D₂)² +(δΡι-δΡ₂)² + (δΗι-δΗ₂)²), where 5Di refers to the dispersion parameter for the solute, 5D₂ refers to the dispersion parameter for the solvent, δΡι refers to the polar parameter for the solute, δΡ₂ refers to the polar parameter for the solvent, δΗι refers to the hydrogen bonding parameter for the solute, and δΗ₂ refers to the hydrogen bonding parameter for the solvent. A small Distance means good compatibility. One software package that uses Hansen Solubility parameters to evaluate suitability of particular solvents or surfactants for a desired application is HSPiP, available at h fp:/ vV\^v.hanse¾--soj¾biIity.cox¾. The HSPiP package has the capability to read a data table containing chemical name and structure encoded as a SMILES string, and to automatically calculate the HSP of the chemical using the so-called Y-MB fragment-based method. This method is used to calculate those compounds that are not included in the HSP database. See, e.g., Charles M. Hansen Hansen Solubility Parameters: A User's Handbook, 2^nd Edition, CRC Press, 2007 and S Abbott, C Hansen, H Yamamoto, Hansen Solubility Parameters in Practice, Software, eBook, Database, v3.1.20,

accessed January 2012 (or v3.1.18 accessed October 201 1), each of which is incorporated herein by reference in its entirety. Like all automatic techniques for estimating molecular properties, the results need to be checked for values that may be numerical artifacts. If HSP parameters are used to evaluate compatibility of a surfactant with another substance, two calculations can be carried out for the surfactant: one for the hydrophobic portion of the surfactant and one for the hydrophilic portion of the surfactant.

[0229] In some embodiments, a Diels-Alder adduct may formed which subsequently undergoes a reverse Diels-Alder reaction to produce a desired species using known techniques.

[0230] Certain Diels-Alder surfactants may be adapted for use in food grade

applications, cosmetic applications, or in medical grade applications. Toxicity and

biodegradability of the compositions incorporating the adducts may be tested according to country-based regulations, local regulations, and/or standards-based tests, and according to anticipated uses (e.g., regulations for substances to come into contact with food to be ingested, substances to be used in food processing equipment, substances to come into contact with the human body, substances to be ingested, or substances to be implanted in the human body).

[0231] In some variations, Diels-Alder surfactants thereof are used as solvents. As described above, hydrophobicity and/or hydrophilicity of the adduct may be tuned to adjust their utility as solvents in a variety of applications. In some embodiments, a Diels-Alder adduct between β-farnesene and a dienophile is used to make surfactants. In some embodiments, Diels- Alder adducts between a-farnesene and dienophiles are used to make surfactants. In some embodiments, Diels-Alder adducts between myrcene and dienophile are used in the applications. It should be understood that the solvents and surfactants described herein may be made from conjugated hydrocarbon terpenes that are not farnesene or myrcene. In some variations, the conjugated terpene used to make a Diels-Alder adduct useful in the applications described herein may for example be any of the C10-C30 conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art. [0232] As described herein, aldehydes, polyaldehydes, esters, diesters, anhydrides, acids or diacids are converted to alcohols or polyalcohols, respectively. In some variations, alcohols or polyalcohols are converted to functionalized or polyfunctionalized surfactants. For example, it is desired to create surfactants (e.g., polyfunctionalized such as di-anionic) that have soil suspending capacity while reducing or minimizing tendency to crystallize or exhibit poor solubility. In some variations, a process is used which is tuned to create a polyalcohol (e.g., a di, a tri, or a tetraalcohol) in addition to or instead of a monoalcohol.

[0233] Surfactants may be formed from aldehyde-containing or alcohol-containing

Diels-Alder adducts by way of any alcohol-to-surfactant or aldehyde-to-surfactant derivatization process known in the industry. Fatty alcohols and aldehydes may be converted into additional surfactants such as cationic surfactants, zwitterionic surfactants (e.g., betaines or amine oxide surfactants), cycloalkylpolyglycoside surfactants, soaps, fatty acids, and/or long-chain alkyl (e.g., di-long-chain alkyl) cationic surfactants. Non-limiting examples of synthetic procedures for obtaining these materials from the parent alcohols or aldehydes may be found in the Kirk Othmer Encyclopedia of Chemical Technology or other suitable references.

[0234] Cationic surfactant, zwitterionic surfactants, amine oxide surfactants,

alkylpolyglycoside surfactants, soaps, fatty acids, may in some variations be combined with nonionic and/or anionic surfactants derived from alcohols. For example, an alcohol may be treated with an alkylene oxide such as ethylene oxide and/or propylene oxide to create an alkoxylated alcohol which may be used in or as a nonionic surfactant, or which optionally may undergo sulfation to create an anionic surfactant.

[0235] Below in are described non-limiting examples of nonionic surfactants, anionic surfactants, cationic surfactants, and zwitterionic surfactants.

NONIONIC SURFACTANTS

[0236] In some cases, the surfactants described herein are nonionic surfactants. Non- limiting examples of nonionic surfactants include alcohols, carboxylic acids, alkoxylated alcohols, acids, or amines (e.g., ethoxylates, propoxylates, or butoxylates), amines,

carboxamides, alkanolamides, sorbitan esters, glycosides, peracids, and glucamides. In certain variations, the nonionic surfactants described herein may have utility as emulsifiers (e.g., for oils used in personal care products, for oils used in agricultural applications, or for oils used in cleaning products), solubilizers, or may be used in detergents (e.g., laundry detergents). In some variations, a nonionic surfactant may be used in combination with one or more additional surfactants.

Alkoxylates

[0237] Alkoxylates may be prepared using known techniques from an alcohol, amine or carboxylic acid. A desired number of moles of an alkylene oxide is reacted with an alcohol, amine or carboxylic acid under known conditions, and a homolog distribution results. In some variations, alcohols can be alkoxylated to form surfactants. The length of the hydrophobic portion of the surfactant can be varied by selection of the hydrocarbon terpene, and the degree of alkoxylation can be varied using known techniques during the alkoxylation process. The hydrophobic portion may include one or more hydrophobic tails having 5-30 carbon atoms attached to a ring structure that is the residue of the Diels-Alder reaction, and the hydrophilic portion may include a polyoxy alkylene chain having about 1 to 200 alkoxylate repeat units. Alkoxylated alcohols, acids, or amines may have applications as detergents, cleaning products, or as emulsifiers or solubilizers (e.g., in personal care products).

[0238] One measure for quantifying the hydrophilic and hydrophobic content of a nonionic surfactant is the Hydrophile-Lipophile Balance (HLB). A low HLB indicates a nonionic surfactant that has high solubility in oil; a high HLB value indicates a nonionic surfactant that has high solubility in water or other polar solvents. HLB value may be selected to lower or minimize the interfacial tension between an oil phase and a water phase.

[0239] HLB values can be calculated for simple alcohol ethoxylates, or measured empirically for other types of nonionic surfactants. HLB is calculated as follows: (molecular weight due to ethoxylate units/molecular weight of molecule) x 100%/5. In operation, HLB values range from about 0.5 to 19.5. HLB values for a mixture of surfactants can be determined as a weighted average of the HLB value for each separate surfactant weighted by the amount of that surfactant in the mixture. In some circumstances, an oil supplier supplies an HLB value for a surfactant (or mixture of surfactants) to be used in applications with that oil (e.g.,

emulsification).

[0240] In some cases, a Diels-Alder adduct surfactant as described herein having an

HLB value in a range from 0-3 is insoluble in water or has limited solubility in water, and has application as a defoaming agent. For mixing unlike oils together, a surfactant having a HLB in a range from about 1 to about 3 may be used. In some cases, a Diels-Alder adduct surfactant having an HLB value in a range from 3-6 is insoluble in water or has limited solubility in water, but is dispersible in water, and has application in forming water-in-oil emulsions. In some cases, a Diels-Alder adduct surfactant having an HLB value in a range from 6-9 is dispersible in water, and has application as a wetting agent, in forming water-in-oil emulsions, or in forming self-emulsifying oils. In some cases, a Diels-Alder adduct surfactant having an HLB value in a range from 8-10 is somewhat soluble in water, and has application as a wetting agent. For making an emulsion by mixing oil into water, a surfactant or blend of surfactants having HLBs in a range from about 8 to about 16 may be used. In some cases, a Diels-Alder adduct surfactant having an HLB value in a range from 10-13 is soluble in water, and has application in forming oil-in-water emulsions, detergents, or cleaning products. In some cases, a Diels-Alder adduct surfactant having an HLB value in a range from 13-15 is soluble in water, and has utility in forming oil-in-water emulsions, detergents, or cleaning products. For solubilizing oils into water, surfactants or surfactant blends having HLBs of about 13 to about 18 may be used. In some cases, a Diels-Alder adduct surfactant having an HLB value that is greater than equal to about 15 is soluble in water, and has application as a solubilizer, detergent, or cleaning product.

[0241] The homo log distribution may vary based on the type of catalyst used in the alkoxylation process. In some variations, an alkoxylation catalyst is selected to result in a narrow or peaked homolog distribution rather than a broad or flat homolog distribution, e.g., a narrow or peaked homolog distribution that is comparable to or narrower than a Poisson distribution. Non-limiting examples of catalysts that may lead to a homolog distribution that is peaked or narrow include calcium-containing catalysts that have been modified by oxyacids or aluminum oxides to result in a narrow distribution of homo logs, calcined hydrotalcite, barium oxides, or calcined aluminum oxide/magnesium oxide (calcined hydrotalcite). Non-limiting examples of suitable calcium-containing catalysts modified by oxyacids are described in US Pat. No. 4,886,917, calcium-containing catalysts modified by aluminum oxides described in US Pat. No. 4,775,657, each of which is incorporated by reference herein in its entirety. Non-limiting examples of calcined hydrotalcite catalysts are provided in German patent DE 03813910, which is incorporated herein by reference in its entirety. Non- limiting examples of barium oxide -based alkoxylation catalysts are provided in US Pat. No. 4,239,917, which is incorporated herein by reference in its entirety.

[0242] In some cases an alkyl-capped alkoxylate is prepared using known techniques.

For example, a methyl-capped, ethyl-capped, propyl-capped or butyl-capped alkoxylate may be prepared. In one example, a methyl ester derivative may be alkoxylated to a methyl-capped ester. In some cases, an alkoxylate having a narrow homolog distribution (e.g., where the alkoxylation is catalyzed using aluminum oxide/magnesium oxide catalysts as described in German patent no. DE 03813910) is used to make an alkyl-capped alkoxylate. Certain esters of ethylene glycol, propylene glycol, and glycerol have HLB values less than 10 and are lipophilic surfactants. Esters may be useful as emulsifiers, e.g., for cosmetics, personal products, or in domestic or industrial applications. In some variations, a combination comprising esters having a low degree of ethoxylation and esters having a high degree of ethoxylation is used as an emulsifier. Esters of ethylene glycol, propylene glycol, and glycerol may be used as emulsifiers, e.g., in personal care products (cosmetics, creams, lotions, ointments, gels). Examples 16 and 17 provide non-limiting examples of alkyl-capped alkoxylates derived from Diels-Alder adducts between β-farnesene and a dienophile.

[0243] In some variations, a Diels Alder adduct that has utility as a nonionic surfactant can be obtained by reacting a conjugated hydrocarbon terpene (e.g., β-farnesene or a-farnesene) with any suitable dienophile that can be converted to an alcohol or diol. For example, any substituted or unsubstituted α,β-unsaturated aldehyde such as:

1 2 3

where each of R , R , and R is independently, H, Ci-Cio alkyl, C3-C6 cycloalkyl, aryl, substituted aryl, and the like; or the dienophile may be an acrylate or substituted acrylate such as:

wherein R¹ is H or Ci-Cg alkyl, and R², R³, and R⁴ are, each independently, H, C1-C10 alkyl, C3- C cycloalkyl, aryl, substituted aryl, and the like. In some variations, allylic alcohols may be used as a dienophile in a Diels-Alder reaction with a conjugated terpene such as β-farnesene or a-farnesene. In some variations, methyl vinyl ketones may be used in a Diels-Alder reaction with a conjugated terpene such as β-farnesene or a-farnesene.

[0244] In some variations, the nonioinic surfactants described herein comprise or are derived from alcohol (J-7-I):

Alcohol (J-7-I) represents any one of, or any combination of the two isomers J-7-IA and J-7-IB shown below:

In some variations, alcohol J-7-I includes both isomers, J-7-IA and J-7-IB. In some variations, alcohol J-7-I includes isomer J-7-IA, with only trace amounts or no detectable amount of isomer J-7-IB. In some variations, alcohol J-7-I includes isomer J-7-IB, with only trace amounts or no detectable amount of isomer J-7-IA. In some variations, alcohol J-7-I includes about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of isomer J-7-IA. Alcohol J-7-I may include any ratio of isomer J-7-IA to isomer J-7-IB. In some variations, alcohol J-7-I includes a ratio of isomer J-7-IA to isomer J-7-IB of about 0.001 : 1, 0.005: 1, 0.01 : 1, 0.05:1, 0.1 : 1, 0.5: 1, 1 : 1, 3: 1, 3.2:1, 3.4: 1, 3.6: 1, 3.8: 1, 4:1, 4.2: 1, 4.4: 1, 4.6:, 4.8: 1, 5: 1, 10: 1, 50: 1, 100: 1, 500: 1, or 1000: 1. Example 9 herein demonstrates the preparation of alcohol J-7-I.

In some variations, compound J-7-II as shown below functions as a nonionic

wherein n represents an average number of ethoxyl repeat units and n is in a range from 1 to 200, from 5 to 30, from 6 to 20, or from 6 to 12, e.g., n=l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. Compound J-7-II represents any one of or any combination of the two isomers J-7-IIA and J-7-IIB as shown below:

[0246] In some variations, compound J-7-II includes both isomers, J-7-IIA and J-7-IIB.

In some variations, compound J-7-II includes isomer J-7-IIA, with only trace amounts or no detectable amount of isomer J-7-IIB. In some variations, compound J-7-II includes isomer J-7- IIB, with only trace amounts or no detectable amount of isomer J-7-IIA. In some variations, compound J -7-II includes 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of isomer J -7-IIA. Compound J -7-II may include any ratio of isomer J -7-IIA to isomer J -7-IIB. In some variations, compound J -7-II includes a ratio of isomer J -7-IIA to isomer J -7-IIB of about 0.001 : 1, 0.005: 1, 0.01 :1, 0.05: 1, 0.1 : 1, 0.5: 1, 1 :1, 3: 1, 3.2: 1, 3.4: 1, 3.6:1, 3.8: 1, 4: 1, 4.2: 1, 4.4: 1, 4.6:, 4.8:1, 5: 1, 10: 1, 50: 1, 100: 1, 500: 1, or 1000: 1. Examples 10, 11, and 12 demonstrate the preparation and characterization of nonionic surfactants of formula (J-7-II), with n=5, 10 and 15, respectively, and HLB=9.0, 12.4, and 14.2, respectively. As shown in the Examples, the surfactants of formula (J-7-II) form stable emulsions with a broad range of commercially important oils used in personal care, agricultural, and cleaning applications. In particular, a surfactant of formula (J-7-II) with n=5 and HLB=9.0 is very effective at forming stable emulsions for oils and waxes used in personal care products that have low polarity and require low HLB surfactants to form stable emulsions. A surfactant of formula (J-7-II) with n=15 demonstrated solubility in electrolyte solutions comparable to that of a corresponding nonylphenol ethoxylates. A surfactant of formula (J-7-II) with n=15 demonstrated laundry detergency effectiveness that exceeded that of a corresponding nonylphenol ethoxylate.

[0247] As described above, some variations of the nonionic surfactants contain alkoxy repeat units that are different than ethoxyl repeat units. For example, some surfactants include propoxyl repeat units in the hydrophilic end, rather than ethoxyl repeat units. Some surfactants include both ethyoxyl and propoxyl repeat units. [0248] Thus, some surfactants are derived from alcohols described herein (e.g., J -7-1 J -

7-V, J -7-VIIA, J -7-VIIB, J -7-IX and have structures analogous to compounds J -7-II, J -7-VI, J -7-VIIIA, J -7-VIIIB and J -7-X, except with propoxy repeat units:

substituted for ethoxy repeat units:

— CH₂ CH₂

The average number m of propoxyl repeat units on these analogs of compound J -7-II, J -7-VI, J -7-VIIIA, J -7-VIIIB and J -7-X can be varied depending on reaction conditions as is known in the art. In some variations of the surfactants, m is in the range 1 to 30. In some variations, m is in the range 5 to 25. In some variations of the surfactants, m is in the range 6 to 20. In some variations, m is in the range 6 to 12. In some variations, m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, m is 9.

[0249] Some variations of surfactants contain both ethoxy and propoxy repeat units, and have structures analogous to compound J -7-II, J -7-VI, J -7-VIIIA, J -7-VIIIB and J -7-X, with the following structure substituted for the ethoxy repeat units:

in which the ethoxy and propoxy repeat units can be distributed in any way along the chain, e.g., as blocks of ethoxyl units grouped together and blocks of propoxyl units grouped together, or with ethoxyl units randomly interspersed among propoxyl units. As is known in the art, the average number p of propoxyl repeat units and the average number q of ethoxyl repeat units can be varied depending on reaction conditions. In some variations of the surfactants, p and q are independently in the range 1 to 30. In some variations of the surfactants, p and q are

independently in the range 6 to 20. In some variations, p and q are independently in the range 5 to 25. In some variations p and q are independently in the range 6 to 12. In some variations, p and q are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,

23, 24, 25, 26, 27, 28, 29 or 30. In some variations, the sum (p+q) is in the range 1 to 30, or 6 to 20, or 5 to 25, or 6 to 12. In some variations, the sum (p+q) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30.

[0250] In some variations, compound J-7-III as shown below functions as a nonionic surfactant:

where the 1,3- and 1,4- isomers of compound J -7-III may be present in any relative amount, and where m represents an average number of propoxyl repeat units and m is in a range from 1 to 30, from 5 to 25, from 6 to 20, or from 6 to 12, e.g., m=l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 1,5 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, compound J-7-III includes the 1,3- isomer with only trace amounts or no detectable amount of the 1,4- isomer. In some variations, compound J -7-III includes the 1,4- isomer with only trace amounts or no detectable amount of the 1,3- isomer. In some variations, compound J -7-III includes a ratio of the 1,3- isomer to the 1,4- isomer of about 0.001 : 1, 0.005: 1, 0.01 : 1, 0.05:1 , 0.1 : 1, 0.5:1, 1 : 1, 3: 1, 3.2:1, 3.4: 1, 3.6: 1, 3.8: 1, 4:1, 4.2: 1, 4.4: 1, 4.6:, 4.8: 1, 5: 1, 10: 1, 50: 1, 100: 1, 500: 1, or 1000: 1.

[0251] In some variations, compound J -7-IV as shown below functions as a nonionic surfactant:

where the 1,3- and 1,4- isomers of compound J-7-IV may be present in any relative amount, and where p represents an average number of propoxyl repeat units and q represents an average number of ethoxyl repeat units, and p and q are each independently in a range from 1 to 30, from 5 to 25, from 6 to 20, or from 6 to 12, e.g., p=l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 and q=l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. The ethoxy and propoxy repeat units can be distributed in any way along the chain, e.g., as blocks of ethoxyl units grouped together and blocks of propoxyl units grouped together, or with ethoxyl units randomly interspersed among propoxyl units. As is known in the art, the average number p of propoxyl repeat units and the average number q of ethoxyl repeat units can be varied depending on reaction conditions. In some variations, compound J-7-IV includes the 1,3- isomer with only trace amounts or no detectable amount of the 1,4- isomer. In some variations, compound J -7-IV includes the 1,4- isomer with only trace amounts or no detectable amount of the 1,3- isomer. In some variations, compound J -7-IV includes a ratio of the 1,3- isomer to the 1,4- isomer of about 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1.

[0252] If methyl vinyl ketone is used as the dienophile in a Diels-Alder type reaction with β-farnesene, after reduction and hydrogenation an alcohol J -7-V can be formed:

Isomers J-7-VA and J-7-VB can be present in any relative amount, e.g., alcohol J-7-V may consist of isomer J -7-VA with no detectable amount of isomer J-7-VB, or may consist of isomer

J-7-VB with no detectable amount of isomer J-7-VA, or a ratio of isomer J -7-VA: J-7-VB may be about 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1,

4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1. Alternatively, alcohol J -7-V can be formed by carrying out a Diels-Alder reaction of β-farnesene with acrolein in the presence of a methyl magnesium halide (e.g. methyl magnesium bromide) or the like. The alcohol J-7-V may be used as is in a formulation in some embodiments, or in other

embodiments, the alcohol may be subsequently alkoxylated to form a surfactant. For example, alcohol J-7-V can be ethoxylated to form surfactant J-7-VI:

Isomers J-7-VIA and J-7-VIB can be present in any relative amount, e.g. surfactant J-7-VI may consist of isomer J-7-VIA with no detectable amount of isomer J-7-VIB, or may consist of isomer J-7-VIB with no detectable amount of isomer J-7-VIA, or a ratio of isomer J-7-VIA: J-7- VIB maybe about 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1. For surfactant J-7- VI, an average number z of ethoxyl repeat units can be in a range from 1 to 30, from 5 to 25, or from 6 to 20, e.g. z=l, 2, 3, 4, 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,21,22, 23, 25,25,26, 27, 28,29, or 30.

[0253] If crotonaldehyde is used as the dienophile in a Diels Alder type reaction with β- farnesene, a mixture of alcohols J-7-VIIA and J-7-VIIB is produced after reduction and hydrogenation of the Diels Alder adducts that are illustrated in Scheme J-7-VII

below:

SCHEME J-7-VII [0254] The resulting alcohol has structure J-7-VIIA and/or J-7-VIIB:

The alcohols J-7-VIIA and J-7-VIIB may be used in a formulation as is in some embodiments, or in other embodiments, may be subsequently treated with an alkylene oxide (e.g., ethylene oxide and/or propylene oxide) to form a mixture of surfactants J-7-VIIIA and J-7-VIIIB (where ethoxylation is shown as a model alkoxylation):

(J-7-VIIIA)

(J-7-VIIIB).

The average number of ethoxyl repeat units y and y' for surfactants J-7-VIIIA and J-7-VIIIB, respectively, is independently in the range of 1 to 30, or 5 to 25, 6 to 20, or 6 to 12. That is, y and y' can each independently be 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, or 30.

[0255] In some variations, nonionic surfactants comprise or are derived from diol J-7-

IX:

[0256] In some variations, the diol J-7-IX is used as is in a formulation, and in other embodiments, the diol may be treated with an alkylene oxide (e.g., ethylene oxide and/or propylene oxide) to form a nonionic surfactant having formula J-7-X (where ethoxylation is shown as a model alkoxylation):

[0257] The average number n of alkoxy (e.g., ethoxy) repeat units in compound J-7-X can be varied depending on reaction conditions as described below. In some variations of the surfactants, n is in the range 1 to 30. In some variations, n is in the range 5 to 25. In some variations of the surfactants, n is in the range 6 to 20. In some variations n is in the range 6 to 12. In some variations, n is 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, n is about 9.

[0258] Non-limiting examples of surfactants having formula (J-7-X) are provided as

Examples 13, 14, and 15, with n=5, 9.2, and 15, respectively, and HLB=12.2, 14.8, and 16.5, respectively. As shown in the Examples, the ethoxylated diol surfactants demonstrate an ability to create stable emulsions with a broad range of oils used commercially in personal care products, agricultural applications, and cleaning applications. The ethoxylated diol surfactants also demonstrate ability to make high, stable foams. The ethoxylated diol surfactants demonstrated good solubility in electrolyte (builder) solutions, and solubility in electrolyte builder solutions that exceeded that of corresponding nonylphenol ethoxylates, which may simplify formulation in cleaning products. The ethoxylated diol surfactants with n=5 and n=10 demonstrated effective laundry detergency that exceeded that of nonylphenol-9.

[0259] It should be understood that analogs of surfactants J-7-VI, J-7-VIIIA, J-7-VIIIB, and J-7-X are contemplated, in which a different alkoxyl repeat unit is substituted in place of some of or all of the ethoxyl repeat units. For example, the alcohols J-7-V, J-7-VIIA, J-7-VIIB, and J-7-IX can be propoxylated instead of ethoxylated, or propoxylated and ethoxylated instead of ethoxylated.

[0260] The alcohols and ethoxylated alcohol nonionic surfactants described herein can be made by any suitable method now known or later developed by one skilled in the art. In some variations, the compounds and surfactants can be made by Diels Alder addition of a dienophile to the diene functionality of the conjugated terpene (e.g., β-farnesene). Non-limiting examples of suitable dienophiles that can be used to produce substituted aldehydes (e.g., 4,8- dimethyl-3,7-nonadienyl-substituted) include: substituted α,β-unsaturated aldehydes such as:

1 2 3

wherein R , R , and R are, each independently, H, Ci-Cio alkyl, C3-C6 cycloalkyl, aryl, substituted aryl, and the like; and acrylates or substituted acrylates such as:

wherein R¹ is H or Ci-Cg alkyl, and R², R³, and R⁴ are, each independently, H, C1-C10 alkyl, C3- C cycloalkyl, aryl, substituted aryl, and the like. In some variations, an allylic alcohol may be used as the dienophile in a Diels-Alder reaction with a conjugated terpene such as β-farnesene or a-farnesene.

[0261] Substituted aldehydes resulting from a Diels-Alder reaction can be reduced to form a substituted alcohol as described above. Any suitable reducing methods and conditions may be used. In some variations, the unsaturated aldehyde (e.g., 4,8-dimethyl-3,7-nonadienyl- substituted aldehyde) is reduced to an unsaturated alcohol (e.g., 4,8-dimethyl-3,7-nonadienyl- substituted alcohol), which is hydrogenated to form the saturated alcohol (e.g., 4,8- dimethylnonyl-substituted alcohol). One non-limiting example of such a method is shown in Example 3, in which the 4,8-dimethyl-3-7-nonadiene substituted aldehyde (28-2) is first reduced using sodium borohydride to form a 4,8-dimethyl-3,7-nonadienyl-substituted alcohol (28-3). The 4,8-dimethyl-3,7-nonadienyl-substituted alcohol is then hydrogenated, e.g., using a palladium catalyst such as Pd/C, a platinum catalyst, or a commercial nickel-based catalyst in a fixed-bed reactor, to saturate double bonds to form a 4,8-dimethylnonyl-substituted alcohol (28- 4), which corresponds to Compound J-7-I above).

[0262] In some variations, the unsaturated aldehyde resulting from the Diels-Alder reaction is reduced to a saturated alcohol (e.g., 4,8-dimethylnonyl-substituted alcohol) in a single step, without forming an unsaturated alcohol intermediate. One non-limiting example of such a process in shown in Example 5. As shown, a catalyst such as a ruthenium catalyst over carbon or a palladium catalyst over carbon can be used to reduce the 4,8-dimethyl-3,7- nonadienyl-substituted aldehyde (28-2) directly to a 4,8-dimethylnonyl-substituted alcohol (28- 4). Such a reaction is described on page 1198 in "March's Advanced Organic Chemistry," by Michael B. Smith and Jerry March, 5^th edition (John Wiley and Sons, Inc., 2001), which is incorporated herein by reference in its entirety as if put forth fully below.

[0263] An alcohol made by any of the methods described above can be further alkoxylated by any method known in the art. Any of the mono-alcohols or diols described herein may be reacted with an alkylene oxide (e.g. , ethylene oxide as shown in Examples 3 and 10-15, or propylene oxide, or both ethylene oxide and propylene oxide) under standard industrial alkoxylation conditions (e.g. sodium hydride, potassium tert-butoxide, or any base having pK>about 16 or 17). The reaction conditions (e.g. time, temperature, pK, concentrations of reagents, solvents) can be varied by any method known in the art to vary the length and/or composition of the alkyloxyl chain. For example, if an alkoxyl chain includes both ethoxyl and propoxyl repeat units, the ratio of ethoxyl to propoxyl repeat units can be controlled by adjusting the ratio of ethylene oxide to propylene oxide during the alkoxylation reaction.

Amines

[0264] In some variations, a nonionic surfactant comprises an amine. For example, an amine surfactant having formula (J-8) may be formed:

where n=l, 2, 3, 4, ..., 10, and the 1,3- and/or 1,4-isomers are present. The amine surfactant (J- 8) may be formed in any suitable manner. For example, for n=l, aldehyde (J-7-I) may undergo reductive amination. For n>l, homologation of the aldehyde (J-7-I) may be carried out using known techniques to reach the desired chain length, followed by amination to form the amine. It should be understood that an amine surfactant may be made in a similar manner using any Diels- Alder adduct described herein comprising an aldehyde group, or any functional group that can be converted to an amine. A primary amine may be alkylated using any suitable technique, e.g., by reaction with an alkyl halide. A tertiary amine may be used to make a quaternary ammonium ion, which may have utility as a cationic surfactant.

Alkanolamides [0265] In some cases, a nonionic surfactant comprises a Diels-Alder adduct derivative that comprises an alkanolamide moiety. For example, a condensation reaction between a Diels- Alder derivative comrpsing a carboxylic acid or a carboxylic acid methyl ester moiety and monoethanolamine, diethanolamine, an N-alkylethanolamine (e.g., N-methylethanolamine or N- ethylethanolamine), an N-alkyldiethanolamine (e.g., N-methyldiethanolamine or N- ethyldiethanolamine), or an Ν,Ν-dialkylethanolamine (e.g., Ν,Ν-diethylethanolamine or N,N- dimethylethanolamine) may be carried out to form a Diels-Alder adduct comprising a alkanolamide and/or an aminoester moiety. For example, a monoalkanolamide having the

structure

esteramide is derived from a Diels-Alder adduct comprising a carboxylic acid or carboxylic acid alkyl ester as described herein. R_DA represents the remainder of the Diels-Alder adduct to which the carboxylic acid or carboxylic acid ester that reacts with the alkanolamine is attached. In one example, an amide ethanolamine is provided by structure (J-9), where the 1,3- and/or 1,4- isomers are formed:

[0266] Secondary alkyl alkanolamines react with a Diels-Alder adduct comprising an acid moiety at elevated temperatures to form alkanolamides, with amine esters and amide esters formed as well. Tertiary alkyl alkanolamines react with an acid at elevated temperatures to form amine esters. Aminoesters may be reacted in the presence of sodium methylate to form an alkanolamide. Alkanolamides may be used as detergents. The terminal hydroxyl group or groups of the alknolamides may be alkoxylated by using any suitable catalyst and reaction conditions. In one variation, an alkanolamide is reacted with ethylene oxide in the presence of sodium methylate to form an alkoxylated alkanolamide. Alkanolamides may be alkoxylated to increase water solubility. Reaction products of acids described herein with monethanolamine, diethanolamine, or alkyl alkanolamines may be used as soaps, detergents, emulsifiers (e.g., in textile lubricants), foam boosters, foam stabilizers, viscosity builders, polishes or waxes for a variety of surfaces (e.g., floors, metal, glass, ceramic, automobile surfaces), surfactants in pesticides, or in personal care products (e.g., hand lotions, shampoos, cosmetic creams, cleansing creams, or shaving creams).

Sorbitan esters

[0267] In one variation, a nonionic surfactant is prepared by the reaction of a Diels-Alder adduct comprising a carboxylic acid or carboxylic acid alkyl ester (e.g., methyl ester) with sorbitol, sorbitan and/or isosorbitol to form esters. Esterification of carboxylic acids described herein or their methyl esters may be carried out under any suitable conditions, e.g., at elevated temperatures (200°C-250°C) in the presence of alkali. For example, monesters, diesters, zwitterion, or tetraesters of sorbitan can be formed.

[0268] One example of a 1 ,4-sorbitan monoester has formula (J-

Compounds having formula (J-10) are derived from a Diels-Alder adduct comprising a carboxylic acid or carboxylic acid alkyl ester moiety. R_DA represents the remainder of the Diels- Alder adduct to which the carboxylic acid or carboxylic acid ester that reacts with 1 ,4-sorbitan is attached. In some instances, sorbitan esters may be alkoxylated (e.g., ethoxylated) to increase water solubility. In certain variations, the esters of sorbitan are not soluble in water, and may have an HLB value below 10. In certain instances, sorbitan esters may be useful as emulsifiers.

Glucosides

[0269] Alkyl glycosides, e.g., alkyl polyglycosides, may be derived from the Diels-Alder adducts described herein. Note that the alkyl portion of the alkyl polyglycoside contains a cyclohexyl ring. Alkyl polyglycosides are nonionic surfactants prepared by glycosidation of Diels-Alder adduct containing an alcohol moiety with a carbohydrate. The term alkyl glycosides as used herein refers to monoglycosides as well as polyglycosides.

[0270] In some variations, an alkyl glycoside has formula (J-l 1):

where

from Diels-Alder adduct attached to the alcohol that reacts with the carbohydrate, and n is 0 to 6, e.g., n=0, 1 , 2, 3, 4, 5, 6.

[0271] The alkyl glycosides may be made by any suitable method known in the art. For example, alkyl glycosides may be prepared from alcohols or polyols described herein (e.g., alcohol (J-7-I) or diol (J-X)) via acid-catalyzed reaction with monosaccharides or

polysaccharides. Non-limiting examples of acid-catalyzed reaction between saccharides and alcohols that may be adapted for use to make the alkyl polyglycosides are described in US Pat. No. 4,950,753, which is incorporated herein by reference in its entirety. The alkyl glycosides may include a hydrophobic hydrocarbon tail having 5-30, 5-20, 5-16, or 5-1 1 carbon atoms. In some variations, the alkyl glycosides have a glucosidic content of about 50%, 55%, 60%, 65%, or 70%). In some variations, alkyl glycosides derived from the Diels-Alder adducts described herein exhibit desirable biodegradability.

[0272] Alkyl polyglycosides derived from the Diels-Alder adducts described herein may be useful for their mildness, foaming ability and/or cold temperature solubility. In some variations, alkyl glycosides are useful in detergents, or in personal care products (e.g., cleansing products, shampoos).

Peracid Surfactants

[0273] In some variations, a neutral surfactant derived from a Diels-Alder adduct as described herein comprises a peracid moiety. A peracid may be prepared using any suitable technique. For example, a Diels-Alder adduct as described herein comprising a carboxylic acid moiety or an acid chloride moiety may be treated with hydrogen peroxide using standard conditions. In some cases, a Diels-Alder adduct comprising a carboxylic acid anhydride (e.g., compound (H-IIIB)) may be reacted with hydrogen peroxide to form compound (J- 12a) and/or (J- 12b):

In some variations, peracid containing surfactants may be buffered, e.g., using any suitable buffer.

Glucamides

[0274] In some variations, glucose can be reacted with an alkylamine (e.g.,

methylamine), which can be reacted with hydrogen to form the N-alkyl glucamine using any suitable catalyst. N-alkyl glucamine can be reacted with a Diels-Alder adduct comprising a carboxylic acid moiety as described herein in the presence of chloromethanoic acid, ethyl ester and pyridine to form an alkylglucamide having formula (J- 13):

where R_DA represents the residue of the Diels-Alder adduct comprising the carboxylic acid that reacts with the N-alkyl glucamine. The alkyl group in the N-alkyl glucamine may be any suitable Ci-Cio alkyl group, e.g., methyl, ethyl, n-propyl, or n-butyl. Alkyl glucamide surfactants may be used as co -surfactants in detergents (e.g., dishwashing or laundry detergents). In some variations, alkylglucamide may be useful for stain removal, or solubilization of co-ingredients.

[0275] In some variations, a Diels-Alder adduct comprising a carboxylic acid group is reacted with isosorbide to form a diester that has utility as a surfactant and/or solvent. Example 19 below provides an example of such a reaction.

ANIONIC SURFACTANTS

[0276] The Diels-Alder adduct derivatives disclosed herein that are useful as surfactants may comprise one or more ionic groups. In some variations, alkali metal carboxylates derived from a Diels-Alder adduct as described herein comprising one, two, or more carboxylic acid moieties are useful as an anionic surfactants. For example, sodium, lithium, manganese, cobalt, nickel, copper, or cadmium salts may be useful as anionic surfactants. [0277] In some embodiments, the Diels-Alder adduct having formula (J-XVIIA) or (J-

XVIIB) has utility as an anionic surfactant:

(J-XVIIB), where n is 1 , 2, 3 or 4; and each of Mi and M₂ is independently a monovalent cation such as Fr+, Cs+, Rb+, K+, Na+, Li+, Ag+, Au+, Cu+, NH4+, primary ammonium, secondary ammonium, tertiary ammonium, or quaternary ammonium, where Mi⁺ and M₂ ⁺may the same or different.

[0278] In certain variations, an alkoxylated (e.g., ethoxylated) alcohol Diels-Alder adduct as described herein is carboxylated, and the carboxylated alkoxylate (e.g., ethoxylate) has utility as an anionic surfactant. For example, an alkoxylated alcohol may undergoes

carboxymethylation to form a carboxylated alkoxylated (e.g., ethoxylate), or a direct oxidative conversion of an ethoxylate to a carboxylic acid may be conducted using radicals such as nitroxide radicals, e.g., as described in U.S. Pat. No. 5,136,103, which is incorporated herein by reference in its entirety.

[0279] In some variations, an anionic surfactant comprising a sulfonate is derived from a

Diels-Alder adduct as described herein. For example, a Diels-Alder adduct comprising a carboxylic acid methyl ester moiety on the hydrophilic section may be reacted with SO₃ at elevated temperatures (e.g., 70-90°C) to form an alpha-sulfonated methyl ester using known techniques. In some variations, a Diels-Alder adduct comprising a carboxylic acid moiety is reacted with sodium 2-hydroxylethyl sulfonate (sodium isethionate) to produce a sulfonated ester.

[0280] In some variations, a halide is derived from a Diels-Alder adduct comprising a primary alcohol group. The halide is reacted with NaS0₃ to form a sulfonate.

[0281] In some variations, an anionic surfactant comprises a sulfate salt. Sulfuric acid esters of alcohols and alcohol alkoxylate derivatives of the Diels-Alder adducts described herein may be prepared. The alcohols can be reacted with S0₃ or sulfamic acid using known techniques to produce the sulfates. [0282] In some variations, an anionic surfactant comprising a sulfosuccinate is derived from a Diels-Alder adduct as described herein. For example, a Diels-Alder adduct having a hydroxyl group (e.g., a Diels-Alder adduct that comprises an alcohol group, an ethoxylate chain terminated with an alcohol group, or an alkanolamide group and represented as RsiOH) may be with maleic anhydride to form a monoester under typical conditions (e.g., a temperature of about 60°C). The monoester may be reacted with a bisulfite (e.g., sodium bisulfite) in the presence of sodium hydroxide, where the pH is adjusted as desired, to form a monoester sulfosuccinate (J- XVIII A) (M+ representing metal counter ion):

(J-XVIIIA).

In some variations, a diester is formed in the first step of the reaction using known techniques (e.g., an esterification catalyst such as p-toluenesulfonic acid) followed by the second step of reaction with a bisulfite to result in a sulfosuccinate diester (J-XVIIIB):

where Rsi may be same or different than Rs₂. In some cases, Rsi is the same as Rs₂. In some cases, Rs₂ is an alkyl group and Rsi is derived from a Diels-Alder adduct comprising a hydroxyl group.

[0283] A sulfosuccinate anionic surfactant may be used in a variety of applications.

Sulfosuccinate monoesters may be used in applications requiring a high degree of foaming, or in personal care products (e.g., shampoos and the like). Sulfosuccinate diesters exhibit weak foaming properties and may be utilized in applications requiring good wetting capability.

Nonlimiting applications of sulfosuccinate surfactant diesters include dispersants, emulsifiers, and surfactants for use in coatings, paints, agricultural applications, and textile manufacture.

CATIONIC SURFACTANTS

[0284] In some variations, a Diels-Alder adduct as described herein comprising a tertiary amine is converted to a quarternary ammonium ion to form a cationic surfactant. Any suitable method may be used to form the quarternary ammonium ion, e.g., by reaction with methyl chloride or dimethyl sulfate. For example, a quaternary ammonium ion may be a Diels-Alder adduct as described herein having the formula R_DA-N (CH₃)₃0^~ may be formed from a Diels- Alder adduct having the formula R_DA-N(CH₃)₂ by reaction with CH₃C1, where R_DA represents the residual of the Diels-Alder adduct that is bonded to the tertiary amine.

[0285] In some variations, cationic surfactants may be derived from aldehydes or alcohols described herein. For example, an alcohol or aldehyde may be converted to a tertiary amine via direct amination via reaction with secondary amines such as monoethanol amine to provide a methyl, hydroxyethyl tertiary amine or via reaction with dimethyl amine to provide a dimethyl tertiary amine. Direct amination may occur in the presence of the reactant amine at about 230°C and 0.1-0.5 Mpa using copper chromite (from an alcohol) or a noble metal, copper chelate, or copper carboxylate catalyst from an aldehyde. Tertiary amines may be converted to a hydroxyalkyl quat or trimethyl quat via reaction with methyl chloride or dimethyl sulfate. Ester quats may be prepared by oxidation of alcohols or aldehydes using any suitable oxidizing agent (e.g., potassium permanganate, Jones reagent, etc.) to form a carboxylic acid, followed by esterification (or diesterification) of N-methyldiethanolamine with the carboxylic acid, followed by quaternization with methyl chloride or dimethyl sulfate.

[0286] In some variations, a fabric softener component comprises a quat-containing

Diel-Alder adduct. Ester quats (e.g., diester quats) and dialkyl quats may be used in fabric softeners.

ZWITTERIONS

[0287] In some variations, a Diels-Alder derivative as described herein having utility as a surfactant comprises a 109witterions. Non- limiting examples of zwitterions include betaines and amine-oxides. In one example, a Diels-Alder surfactant comprising a betaine has formula (J- 14 A) and/or (J-14B):

where R and R' are independently any suitable alkyl group, e.g., a CI -CIO alkyl group such as methyl, ethyl, n-propyl, or n-butyl.

[0288] A Diels- Alder adduct as described herein as a betaine may be prepared using any suitable method. For example, a maleic anhydride adduct (e.g., compound H-IIIB) may be opened with an amine having formula NHRR' to form a carboxamide group and the carboxylic acid group attached to the ring. The carboxamide may be selectively reduced to form the amine group. In other variations, to prepare zwitterionic betaine surfactants, tertiary amines may be reacted with a substituted or unsubstituted 1 ,3-sultone, e.g., in acetone. Zwitterionic surfactants may be useful in enhancing cold water performance and/or formulability.

[0289] An amine-oxide may be produced from a Diels-Alder adduct as described herein comprising a dialkyl amine (e.g., dimethyl amine) moiety by oxidation using known techniques. For example, a Diels-Alder adduct substituted with a dimethyl amine moiety may be reacted with peroxide. A Diels-Alder adduct amine oxide has the formula (J- 15):

N⁺Cr

^ RDA (j-15) and is derived from a Diels-Alder adduct as described herein having the formula R_DA-N(CH3)₂. Alternatively, an amine oxide is prepared from a tertiary amine by oxidizing the peroxide in water with a bicarbonate buffer.

[0290] Incorporated in personal care products such as shampoos, amine oxides may be used to modify viscosity, reduce eye irritancy, and enhance foam properties of a composition. Amine oxides may be especially suitable in slightly acidic or neutral formulas. In domestic cleaners, amine oxides may be used in association with anionics in some variations. Amine oxides may be used in industrial applications such as liquid bleach products, surfactants used in textile processing, foam stabilizers and anti corrosion formulations. Amine oxides may be used in formulations in which grease cleaning and/or foaming ability is desired.

PHYSICAL PROPERTIES OF SURFACTANTS

[0291] In certain variations, the critical micelle concentration of the nonionic surfactants described herein is about 100 ppm or lower, e.g., about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,

60, 65, 70, 75, 80, 85, 90, 95, or 100 ppm. In some variations, a Diels-Alder adduct having formula (J-7-X), wherein n is in a range from about 5 to about 15 ethoxylate units (e.g., 5, 10, or 15 ethoxlate units) has a cmc of about 20 ppm or less, e.g., about 20, about 15, about 10, or about 5 ppm. In some variations, a Diels-Alder adduct having formula (J-7-X), where n is in a range from about 5 to about 20 ethoxylate units (e.g, 5 or 10 ethoxylate units) has a cmc of about 10 ppm or less, e.g., about 10, about 5, about 4, or about 3 ppm. In some variations, a Diels- Alder adduct having formula (J-7-II), wherein n is in a range from about 5-15 ethoxylate units has a cmc of about 20 ppm or less, e.g., about 20, 15, or 10 ppm.

[0292] In some variations, the surface tension of the nonionic surfactants described herein (e.g., surfactants having formula (J-7-II) or (J-7-X), with n in a range from about 5 to about 15) is in a range from about 25 to about 50 mN/m at 0.01% in distilled water and at 25°C. For example, the surface tension of a nonionic surfactant may be about 25, 30, 35, 40, 45, or 50 mN/m at 0.01% and 25°C.

[0293] In some variations, the nonionic surfactants described herein may be used as an effective emulsifier for a broad range of oils used in agricultural, personal care, and cleaning applications, e.g., nonpolar hydrocarbons, esters, and fatty alcohols. Mineral spirits, xylene, and soy methyl ester may be used individually or in combination in emulsifiable concentrates in agricultural products. Mineral oil, cetyl alcohol, and C8-C10 triglyceride may be used individually or in combination in personal care products. Mineral spirits, pine oil and d- limonene may be used individually or in combination in domestic and industrial cleaning products. For example, the nonionic surfactants described herein (e.g., surfactants having formula (J-7-II) or (J-7-X), with n in a range from about 5 to about 15 such as about 5, 10, or 15) may be an effective emulsifier for mineral oil, mineral spirits, xylene, triglycerides (e.g., C8-C10 triglyceride), cetyl alcohol, soy methyl esters, pine oil, or d-limonene.

[0294] In certain variations, surfactants described herein form stable emulsions with oils and waxes used in personal care formulations. Oils and waxes used in personal care products may have low polarity and require low HLB surfactants or low HLB for a combination of surfactants to form stable emulsions. Certain surfactants described herein (e.g., surfactants having formula (J-7-II) or (J-7-X) with n in a range from about 5 to about 15, such as about 5, 10, or 15) may form stable emulsions with mineral, C8-C10 triglyceride, cetyl alcohol, myristyl myristate, or C12-C15 benzoate. A surfactant of formula (J-7-II) with n=5 may form a stable emulsion with the above-listed oils used in personal care products at about 5%> or less. A surfactant of formula (J-7-II) with n= 10 or 15 may form a stable emulsion with the above-listed oils used in personal care products at about 10%> or less. A surfactant of formula (J-7-X) with n=5, 10, or 15 may form a stable emulsion with the above-listed oils used in personal care products at about 10% or less.

[0295] In some variations, a single nonionic surfactant as described herein may be used as an emulsifier as described above. In some variations, a combination of two or more nonionic surfactants described herein is used as an emulsifier. In some variations, a combination of one or more nonionic surfactants as described herein and one or more co-emulsifiers is used to form stable emulsifications with a desired hydrocarbon, ester, or fatty alcohol. In some instances combinations of surfactants with differing HLBs may be more effective emulsifiers than individual surfactants used alone. In some variations, an emulsifier comprises a first surfactant having a first HLB and a second surfactant having a second HLB, wherein the first HLB is at least about 1 , at least about 2, at least about 3, at least about 4, or at least about 5 HLB units different from the second HLB. At least one of the first and second surfactants in the emulsifier is derived from a Diels-Alder adduct between a conjugated hydrocarbon terpene and a dienophile, as described herein. In some variations, each of the first and second surfactants in the emulsifier are derived from the Diels-Alder adducts described herein. In some variations, an emulsifier may comprise a combination of two or more of the surfactants of Examples 10-15, e.g., a combination comprising two surfactants that have HLB values that differ by more than about 1 HLB unit, more than about 2 HLB units, more than about 3 HLB units, more than about 4 HLB units, or more than about 5 HLB units.

[0296] In some variations, a nonionic surfactant as described herein show tolerance to builders that are typically used in domestic or industrial cleaners to provide alkalinity and soil dispersion. For example, the nonionic surfactants as described herein (e.g., surfactants of formula (J-7-II) or (J-7-X) with n in a range from about 5 to about 15, such as about 5, 10 or 15) may tolerate up to about 10%> potassium tripolyphosphate (TKPP) (e.g., about 5%>, 6%>, 7%>, 8%>, 9%), or 10%)), up to about 6%> sodium metasilicate (e.g., about 3%>, 4%>, 5,%>, or 6%>), or up to about 8%o potassium hydroxide (e.g., about 3%>, 4%>, 5%>, 6%>, 7%>, or 8%>). Solubility in electrolytes may simplify formulation of cleaning products, e.g., laundry detergents. In some cases, the surfactants described herein (e.g., the surfactants of Examples 10-15 may reduce or prevent formation of gels when the surfactants are added to water. The ethoxylated alcohol surfactants described herein (e.g., those having formula (J-7-II) or (J-7-X)) may exhibit improved solubility, tolerance to builders, or detergency (e.g., laundry detergency) as compared with an ethoxylated alcohol surfactant exhibiting the same number of carbons in the hydrophobe but having a less branched hydrophobe (e.g., a linear alkyl hydrophobe). [0297] Laundry detergency of surfactants and surfactant compositions described herein can be measured using any suitable method. In some variations, change in reflectance of a soiled cloth before and after laundering under known conditions (e.g., using a Terg-O-Tometer) is used to evaluate laundry detergency. In some variations, a laundry detergency of the nonionic surfactants as described herein (e.g., surfactants of formula (J-7-II) or (J-7-X) with n in a range from about 5 to about 15, such as about 5, 10 or 15) is such that a cloth (cotton or durable press) soiled with dust-sebum exhibits an increase in reflectance (difference between % reflectance measured before washing and % reflectance measured after washing) of up to about 20% (e.g., about 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%) following cleaning using a formulation comprising 10% surfactant and a component to provide alkaline buffering (e.g., about 2% soda ash). In some variations, performance of a laundry detergent comprising a surfactant described herein is evaluated using ASTM D4265-98 (reapproved 2007) "Standard Guide for Evaluating Stain Removal Performance in Home Laundering," published by ASTM International, which is incorporated herein by reference in its entirety. In some variations, performance of a laundry detergent is evaluated by measuring using HunterLAB coordinates L, a, and b, or CIE (International Commission on Illumination) coordinates L*, a*, and b*, where L and L* are lightness parameter in which L=0 or L*=0 represents a specimen that appears black to the human eye, L=100 or L*=100 represents a specimen that appears diffuse white, a or a* represents a value between red and green (with negative values indicating green and positive values indicating red), and b or b* represents a value between yellow and blue (with negative values indicating blue and positive values indicating yellow). See, e.g., HunterLAB. Application Notes, Insight on Color August 1-15, 1996, Vol. 8, No. 9 (available at ^ ^^ ^^SMQ% and Commission Internationale de L'Eclairage at .ds,co .at. L, a, and b and L*, a*, b* can be measured using any standard colorimetric technique using any suitable apparatus. A change in color for stained fabric before and after laundering may be

2 2 2 1/2

evaluated as delta E = {(Li-L₂) +(a₁-a₂) +(bi-b₂) } , where LI, al and bl are the initial values of a article to be cleaned, and L2, a2 and b2 are the final values of an article after cleaning. It should be noted that an analogous quantity delta E* may be evaluated if L*, a*, and b* color coordinates are used instead of L, a, b: delta E*={(Li*-L₂*)²+(ai*-a₂*)²+(bi*-b₂*)²}^1/2. In some variations, a laundry detergent incorporating an effective amount of surfactant as described herein (e.g., a surfactant having formula (J-7-II) or (J-7-X) with n in a range from about 5 to about 15, such as about 5, 10 or 15), may exhibit a delta E or delta E* of at least about 3, at least about 4 or at least about 5 when treating grass stain on a poly-cotton blend fabric; delta E or delta E* of at least about 5, 6, 7, 8, 9, 10 or 11 when treating a blood/milk/carbon stain on a cotton fabric; delta E or delta E* of at least about 6, at least about 7, at least about 8, at least about 9, at least about 10, or at least about 11 when treating ground in clay on a cotton fabric; delta E or delta E* of at least about 10, at least about 11, at least about 12, at least about 13, or at least about 14 when treating a blood stain on cotton; delta E or delta E* of at least about 10, at least about 11, at least about 12, at least about 13 when treating a red wine stain on a cotton fabric; at least about 12, at least about 13, at least about 14, at least about 15, or at least about 16 when treating a tomato/beef sauce on a cotton fabric; delta E or delta E* of at least about 0.2, at least about 0.3, at least about 0.4, at least about 0.5, at least about 0.6, at least about 0.7, at least about 0.8, at least about 0.9, or at least about 1 when treating a coffee stain on cotton; delta E or delta E* of at least about 3, at least about 4, at least about 5, at least about 6, at least about 7, or at least about 8 when treating a cocoa stain on cotton fabric; or a total delta E or total delta E* representing the sum of delta E values or delta E* values, respectively, observed for a representative set of stained cloth swatches of at least about 50, at least about 55, at least about

60, at least about 65, at least about 68, at least about 70, at least about 72, or at least about 75.

One non-limiting example of a representative set of stained cloth swatches includes a grass stain on poly-cotton, blood/milk/carbon stain on cotton, ground-in clay on cotton, blood on cotton, red wine on cotton, tomato/beef sauc on cotton, coffee on cotton, and cocoa on cotton An effective amount of surfactant in a liquid laundry detergent may be about 5-20 wt%, about 5-15 wt%, about 10-15 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, about 19 wt%, or about 20 wt%, based on the total composition of the detergent.Hard surface detergency of surfactants and surfactant compositions described herein can be measured by any suitable method. In some cases, hard surface detergency is measured using ASTM D4488-95 A5 "Standard Guide for Testing Cleaning Performance of

Products Intended for Use on Resilient Flooring and Washable Walls" (reapproved in 2001 and withdrawn in 2009 by ASTM) (also referred to as ASTM D4488 A5 herein), which is incorporated herein by reference in its entirety. ASTM D4488-95 A5 involves soiling white vinyl floor tile with a mixture of oily and particulate soils, and cleaning with detergent-saturated sponges in a Gardner Scrubbability Apparatus. In some variations, a hard surface detergency as evaluated by ASTM D4488-95 A5 using a formulation including an effective amount (e.g., 5%) surfactant described herein (e.g., a surfactant having formula (J-7-II) or (J-7-X) with n in a range from about 5 to about 15, such as about 5, 10 or 15) and 10% TKPP at 1/64 dilution (2 oz/gal) increases reflectance at 45 degrees (on a black-white scale) of tiles soiled with a mixture of oily and particulate soils by at least about 84% (e.g., about 84%, 85%, 86%, 87%, 88%, 89%, or 90%), and at 1/128 dilution (1 oz/gal) increases reflectance at 45 degrees (on a black-white scale) by at least about 80% ( e.g., about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%o, or 90%)). In some cases, hard surface cleaning may be evaluated using HunterLAB coordinates L, a , and b or CIE coordinates L*, a*, and b* as described above. Reflectance of white vinyl tiles before and after soiling may be measured using any suitable colorimeter using any suitable light source (e.g., a CIE standard D65 illuminant). In some variations, only L* values are used to evaluate reflectance (e.g., at 0° and/or at 45°) on a black-white scale.

Cleaning efficiency can be measured as follows: % cleaning efficiency=(R^c-R^s)/(R°-R^s) x 100%, where R°=original reflectance, R^c=cleaned reflectance, and R^s=soiled reflectance. In some variations, a detergent for hard surface cleaning that comprises a surfactant described herein (e.g., a surfactant having formula (J-7-II) or (J-7-X) with n in a range from about 5 to about 15, such as about 5, 10 or 15) exhibits a cleaning efficiency of at least about 40%, at least about 45%, or at least about 50% at a dilution of 1/128 in unheated tap water.

[0298] In some surfactant compositions, a hydrotrope is added to improve the solubility of surfactants in aqueous solution. Nonlimiting examples of hydrotropes include sodium benzene sulfonate, sodium toluene sulfonate, sodium xylene sulfonate (SXS), sodium cumene sulfonate, and sodium cymene sulfonate. A hydrotrope and amount of hydrotrope can be selected based on the quantity of builders and other electro lyes in the solution. The level of builders or other electrolytes may lower cloud point or solubility of certain surfactants in aqueous solution, and hydrotropes can be used to achieve a desired cloud point. Generally, increasing a quantity hydrotrope in a solution increases cloud point. A surfactant composition comprising a nonionic surfactant described herein (e.g., surfactants of formula (J-7-II) or (J-7-X) with n in a range from about 5 to about 15, such as about 5, 10 or 15, and especially the surfactants of formula (J-7-X) with n in a range from about 5 to about 15, such as about 5, 10, or 15) may require reduced quantity of hydrotrope or no hydrotrope to achieve a suitable cloud point, as compared with aqueous solutions utilizing conventional nonionic surfactants (e.g., NEODOL™ surfactants). For example, an aqueous solution comprising an effective amount of surfactant having formula (J-7-X) with n in a range from about 5 to about 15 for a cleaning application (e.g., hard surface cleaner) may exhibit a cloud point of at least about 50°C (e.g., about 50°C or about 55°C, or even higher) without the need for a hydrotrope.

K) APPLICATIONS

[0299] The surfactants described herein can be formulated into a variety of compositions adapted to specific purposes. For example, surfactants described herein can be included in formulations as emulsifiers, solubilizers, solvents, wetting agents, dispersants, anti-foam agents, foaming agents, detergents (e.g., laundry detergents, dishwasher soaps and the like), antistatic agents, industrial and household cleaning products (e.g., floor and other surface cleansers, bathroom cleansers, furniture cleansers, degreasers, and the like), fabric care products, oil recovery surfactants, and personal care products (e.g., cleansing bars and liquids, hair care products, moisturizers, dental care products, emollients, humectants and the like).

[0300] Surfactant compositions can be formulated into any suitable type of composition or package. Surfactant compositions can be homongeneous or nonhomogeneous, and single phase or multiphase. Nonlimiting examples of forms that surfactant compositions may take include solids such as powders, granules or large particles, tablets, bars, and the like; liquids; gels; pastes; emulsions; sprays; foams; wet wipes; dry wipes that are activated by use with water by a consumer; and multipart packages that combine separated components upon use.

[0301] Any mixing or dispersing equipment known to a person of ordinary skill in the art may be used for blending, mixing or solubilizing the ingredients. The blending, mixing or solubilizing may be carried out with a blender, an agitator, a disperser, a mixer (e.g., Ross double planetary mixers and Collette planetary mixers), a homogenizer (e.g., Gaulin

homogenizers and Rannie homogenizers), a mill (e.g., colloid mill, ball mill and sand mill) or any other mixing or dispersing equipment known in the art.

[0302] In some variations, a Diels-Alder adduct as described herein may be used as a nonionic surfactant. The surfactants described herein include a hydrophilic portion that is soluble in water, including cold water in some variations, and a hydrophobic portion that can solubilize and efficiently remove oily soils (oil, fatty substance, grease, clay, and the like). Some of the surfactants described herein may demonstrate rapid water-oil interface kinetics so as to be able to effectively remove soil within a short wash time. In some cases, a Diels-Alder adduct may be modified so as to form an anionic or cationic compound that has utility as a surfactant. For example a Diels-Alder adduct incorporating one or more carboxylic acid salts may be made, a sulfate may be formed (e.g., using standard sulfation techniques such as SOs/oleum sulfation), a phosphate or phosphite may be formed, or an ammonium ion may be made. Cationic Diels-Alder adducts (e.g., ammonium ions such as quaternary ammonium ions) and anionic Diels-Alder adducts (e.g., sulfates or phosphates) may be useful as surfactants in applications such as soaps, detergents, wetting agents, dispersants, emulsifiers, foaming agents, antistatic agents, corrosion inhibitors, and antimicrobials. [0303] Certain anionic surfactants derived from Diels-Alder adducts may be useful in detergents, soaps, builders and other cleaning agents, emulsifiers and the like. Certain cationic surfactants derived from the Diels-Alder adducts described herein may have use in personal care products. For example, ammonium ions (e.g., quaternary ammonium ions) may have use in hair products such as shampoos, conditioners and the like. Ammonium ions (e.g., quaternary ammonium ions) may be useful as dye sites, antimicrobials, and herbicides. N-oxides formed from the Diels-Alder adducts described herein may have use as surfactants, e.g., for use in personal care products (e.g., shampoos, conditioners, and the like).

[0304] In some variations, anionic surfactants may be used at levels as high as about 30 to 40% of a detergent formulation. Other important surfactants used in consumer products include amine oxides, cationic surfactants, zwitterionic surfactants, alkyl polyglycoside surfactants, soaps, and fabric softening cationic surfactants. These additional types of surfactants provide additional cleaning benefits over those provided by anionic surfactants, as well as enhanced foaming, enhanced skin mildness, and fabric softening. The conjugated terpene and/or post-Diels-Alder reaction chemical modification may be selected to design surfactants that provide enhanced cold water cleaning performance, enhanced cleaning performance in general, and process and/or rheological advantages. In some variations, it is desired that materials be readily biodegradable and substantially derived from biomaterials to make consumer products.

[0305] Non-limiting examples of industrial applications for surfactants described herein include paper processing, textile processing, commercial laundering, hard surface cleaning, corrosion inhibition, metal working fluids, enhanced oil recovery, drilling fluid, asphalt emulsions, emulsion polymerization, emulsion breaking, and agricultural applications (e.g., to improve wetting, spreading and effectiveness of herbicides, fungicides, insectides, and the like), and pharmaceutical uses (cleansing, coatings, lotions).

[0306] In some variations, the surfactants described herein have utility as cleaners

(domestic or industrial). Desired properties include detergency (soil removal), suspension of particulate soil, emulsification of oily soils, soil dispersion properties, reduction of tendency of soil to redeposit, aqueous solubility, solubility in electrolytes (builders), low sensitivity to water hardness, low sensitivity to water temperature. For laundry detergents, the surfactants function to remove soil from fabrics and suspend the soil in the wash solution. Surfactant or blend of surfactants may be selected on laundry conditions (e.g., water temperature, water hardness, water temperature, wash cycle, amount of water). In some variations, anionic surfactants are useful for removing particulate soils. In some variations, nonionic surfactants are useful for removing oily soils. Combinations of anionic surfactants and nonionic surfactants may be used in laundry detergent formulations. Laundry detergent formulations may include bleaches or enzymes for stain removal.

[0307] In certain variations, cationic surfactants described herein have utility as fabric softeners, e.g., Diels- Alder adducts comprising quaternary ammonium ions.

[0308] In certain variations, the surfactants described herein comprise hard surface cleaners, sanitizing cleaners, dishwashing detergents, floor cleaners, or carpet cleaners.

[0309] In certain embodiments, the surfactants have use in personal care products. For example, alcohol surfactants, alkyl glycosides, or zwitterionic surfactants described herein may have use in shampoos, baby wipes, body washes, and the like. In some personal care formulations, a primary surfactant is combined with a zwitterionic surfactant.

[0310] A surfactant described herein can be present in a formulation in any suitable amount. Depending on the application, a surfactant described herein may be present in an amount in a range from about 0.01 wt.% to about 99.99 wt.%, about 0.1 wt.% to about 99.9 wt.%), about 1 wt.%) to about 99 wt.%, about 5 wt.% to about 95 wt.%, about 10 wt.% to about 90 wt.%, about 20 wt.% to about 80 wt.%, from about 30 wt.% to about 70 wt.%, from about 40 wt.% to about 60 wt.% in a formulation, from about 1% wt.% to about 50%wt.%, from about 1%) wt.%) to about 40wt.%, from about 1 wt.% to about 30wt.%, from about 1 wt.% to about 20wt.%, from about 1 wt.% to about 10 wt.%, where wt.% refers to the weight of the surfactant as a percent of the total weight of the formulation. In some formulations, a surfactant described herein is present in an amount as small as about 1 wt.%, 0.5 wt.%, 0.1 wt.%, or even smaller, e.g. about 0.01 wt.% or 0.05 wt.%. In some formulations, a surfactant described here is present in an amount of about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, 99.9, or 99.99 wt.% of the total formulation.

[0311] Within each of these broad purposes, formulations comprising the surfactants described herein can be adapted for certain applications. For example, laundry detergents comprising the surfactants described herein can be developed to remove soil under a variety of laundry conditions, such as varied cycle time (e.g., cycle times as short as 15-20 minutes to cycle times as long as multiple hours), varied water conditions (e.g., hot or cold water, hard or soft water), water level (e.g., high volume water wash as in conventional washing machines to low volume water wash as used in high efficiency washing machines), washing machine design

(e.g., degree of agitation) and hand washing. [0312] The formulations comprising the surfactants describe herein can optionally comprise additional components. For example, detergents comprising one or more surfactants described herein can additionally comprise any one of or any combination of builders, enzymes, enzyme stabilizers, polymer additives, bleaching agents, colorants, dye transfer inhibitors, chelating agents, rheological modifiers, pearlescent agents, colorants or pigments, fragrances, solvents, effervescents, optical brighteners, fluorescers, soil release polymers, dispersants, suds suppressors, photoactivators, preservatives, antioxidants, antishrink agents, gelling agents, antiwrinkle agents, germicides, fungicides, antideposition agents, sunscreens, clays, luminescent agents, anticorrosion or other appliance protection agents, solubilizers, processing aids, pH modifiers, and free radical scavengers. In some variations, detergents comprise one or more surfactants described herein and one or more builders, one or more enzymes, and one or polymer additives. A component combination with the surfactants described herein can be selected from those builders, enzymes, enzyme stabilizers, polymer additives, bleaching agents, colorants, dye transfer inhibitors, chelating agents, rheological modifiers, pearlescent agents, colorants, fragrances and solvents that are known in the detergent industry. In some variations of detergents made using one or more surfactants described here, the surfactant comprises at least about 5wt.%, 10wt.%, 15%, 20wt.%, 25wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.% , 50 wt.%, 55 wt% 60wt%, 65 wt%, or 70wt%, based on the total active ingredients of the detergent. In some variations, liquid detergent formulations may contain as much as 70% nonionic surfactant, based on the total active ingredients of the detergent. In some variations, dry detergent formulations may contain 5-30wt% nonionic surfactant, based on the total active ingredients of the detergent. In some formulations, more than one surfactant is present, e.g. a nonionic surfactant as described herein, and one or more additional surfactants (e.g. one or more anionic surfactants).

[0313] In certain embodiments and depending on application, formulations comprising the surfactants described herein comprise any one of or any combination of the following non- limiting examples of additives: corrosion inhibitors, thickeners, colorants, fragrances, stabilizers, antioxidants, odorants, additional surfactants, stabilizers, emollients or humectants.

[0314] A compound, composition, or surfactant described herein is used as a substitute for a nonylphenol or alkoxylated nonylphenol (e.g., a nonylphenol ethoxylate) in some formulations. For example, alcohol J-7-I, J-7-V, J-7-VIIA, J-7-VIIB, or J-7-IX as described above may be used as a substitute for a nonylphenol ethoxylate in some formulations. In other formulations, compound J-7-II, J-7-VI, J-7-VIIIA, J-7-VIIIB, or J-7-X as described above (e.g., with n being about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, or 15) can be used as a substitute for an nonylphenol ethoxylate, e.g., NP-9 or NP-12. When using a composition or surfactant described herein as a substitute for a nonylphenol ethoxylate, the composition or surfactant described herein can in some circumstances be used as a direct replacement for the nonylphenol ethyoxylate, while in other circumstances, the amount of surfactant substituted for the nonylphenol ethoxylate may be different, or one or more additives (e.g., an additional surfactant such as an anionic surfactant) may be used in combination with the surfactant described herein to substitute for the nonylphenol ethoxylate.

[0315] In some variations, certain of the Diels- Alder adduct as described herein have utility as surfactants that can act as peroxide accelerators. In some variations, certain of the Diels-Alder adducts described herein have utility as a surfactant for rubber emulsion (e.g., styrene-butadiene rubber or natural rubber latex) polymerization. For example, a Diels-Alder adduct that comprises one or more carboxyl groups may be used as an aid in rubber emulsion polymerization.

[0316] In some variations, a cleaning composition comprises one or more Diels-Alder adduct surfactants as described herein in an amount ranging from about 0.001 wt% to about 100 wt %. The Diels-Alder adduct surfactants as described herein can be selected to have desired functionality to form cleaning compositions for certain applications. Nonlimiting examples of cleaning compositions include laundry cleaning products, dishwashing detergents (hand or automatic dishwasher), household or industrial hard surface cleansers (e.g., floors, countertop, windows, bathrooms, and the like), and personal cleaning products. Formulations comprising the surfactants described herein may be adapted for any form factor, e.g., liquids, gels, pastes, powders, granules, solids, tablets, bars, sheets, sprays, foams, and the like. Laundry cleaning products include laundry detergents and laundry aids such as fabric conditioners, stain treatments, presoaking formulations, bleaches, and the like. Laundry cleaning products may be adapted to treat certain types of fabrics or constructions and may be adapted for a variety of different laundering conditions (e.g., cold water wash, hard water conditions, low water volume wash, degree of soil, degree of agitation, etc.) Dishwashing formulations may provide effective greasy soil removal as well as antistreaking and ingredients for skin care. Automatic dishwasher formulations may be adapted for a variety of different dishwasher configurations (e.g., water temperature, water hardness, water volume, cycle time, degree of agitation, drying cycles and the like) and provide effective soil removal as well as minimal or no residue formation and minimal or no streak formation. Personal cleaning products comprise shampoos, conditioners, shaving cream, body washes, toothpastes, and the like. Besides effective cleaning, aesthetic and sensorial effects (e.g., greasy or silky feel, lather, odor, sudsing, rinsability, color) may be important for personal cleaning formulations.

[0317] In some variations, a cleaning composition comprises about 0.001 wt% to about

100% wt% of a Diels-Alder adduct surfactant as described herein that is an alcohol or a polyol. In certain variations, a cleaning composition comprising a Diels-Alder alcohol or polyol further comprises one or more cosurfactants. Such one or more cosurfactants can be any one of or any combination of the cationic, anionic, nonionic, or zwitterionic surfactants as described herein, or may include any other cationic, anionic, nonionic or zwitterionic surfactant known in the art.

[0318] In some variations, a cleaning composition comprises about 0.001 wt% to about

100 wt% of a Diels-Alder adduct surfactant as described herein that is a carboxylic acid or diacid, or a salt thereof. In certain variations, a cleaning composition comprising a Diels-Alder carboxylic acid or diacid further comprises one or more cosurfactants. Such one or more cosurfactants can be any one of or any combination of the cationic, anionic, nonionic, or zwitterionic surfactants as described herein, or may include any other cationic, anionic, nonionic or zwitterionic surfactant known in the art.

[0319] In some variations, a cleaning composition comprises about 0.001 wt% to about

100 wt% of a Diels-Alder adduct surfactant as described herein that is a glucoside or

diglucoside. In certain variations, a cleaning composition comprising a Diels-Alder glucoside or diglucoside further comprises one or more cosurfactants. Such one or more cosurfactants can be any one of or any combination of the cationic, anionic, nonionic, or zwitterionic surfactants as described herein, or may include any other cationic, anionic, nonionic or zwitterionic surfactant known in the art.

[0320] In some variations, a cleaning composition comprises about 0.001 wt% to about

100 wt% of a Diels-Alder adduct surfactant as described herein that is a glucamide or diglucamide. In certain variations, a cleaning composition comprising a Diels-Alder glucamide or diglucamide further comprises one or more cosurfactants. Such one or more cosurfactants can be any one of or any combination of the cationic, anionic, nonionic, or zwitterionic surfactants as described herein, or may include any other cationic, anionic, nonionic or zwitterionic surfactant known in the art.

[0321] In some variations, a cleaning composition comprises about 0.001 wt% to about

100 wt% of a Diels-Alder adduct surfactant as described herein that is a cationic surfactant. In certain variations, a cleaning composition comprising a Diels-Alder cationic surfactant further comprises one or more cosurfactants. Such one or more cosurfactants can be any one of or any combination of the cationic, anionic, nonionic, or zwitterionic surfactants as described herein, or may include any other cationic, anionic, nonionic or zwitterionic surfactant known in the art.

[0322] In some variations, a cleaning composition comprises about 0.001 wt% to about

100 wt% of a Diels-Alder adduct surfactant as described herein that is a anionic surfactant. In certain variations, a cleaning composition comprising a Diels-Alder anionic surfactant further comprises one or more cosurfactants. Such one or more cosurfactants can be any one of or any combination of the cationic, anionic, nonionic, or zwitterionic surfactants as described herein, or may include any other cationic, anionic, nonionic or zwitterionic surfactant known in the art.

[0323] In some variations, a cleaning composition comprises about 0.001 wt% to about

100 wt% of a Diels-Alder adduct surfactant as described herein that is a zwitterionic surfactant. In certain variations, a cleaning composition comprising a Diels-Alder zwitterionic surfactant further comprises one or more cosurfactants. Such one or more cosurfactants can be any one of or any combination of the cationic, anionic, nonionic, or zwitterionic surfactants as described herein, or may include any other cationic, anionic, nonionic or zwitterionic surfactant known in the art.

[0324] In some variations, one or more enzymes are included in effective amounts in surfactant compositions. For example, laundry detergents, laundry aids, dishwashing detergent (e.g., for automatic dishwashers), or industrial cleaner formulations may comprise one or more detergent enzymes in an effective amount. In some instances, a single enzyme is used in a formulation. In some instances, two different enzymes are used in a formulation. The presence of one or more enzymes may improve cleaning performance of the composition and/or provide fabric conditioning. Diels-Alder surfactants can be selected to be compatible with enzymes that are present in the formulation. Non-limiting examples of suitable enzymes include proteases, lipases, amylases, cellulases, mannanases, pectinases, arabinases, galactaneses, xylanases, oxidases, peroxidases, and mixtures of two or more of the foregoing. In some variations of detergents (e.g., laundry or dishwashing) or stain treatment formulations an enzyme (e.g., a protease) is selected to be effective at soil removal in cold water. If a protease is used, it can be derived from animals or vegetables, or be microbially-derived. Proteases may be included in certain detergent formulations (e.g., laundry or dishwashing) or stain treatments in which it is desired to remove protein residues or stains (e.g., milk, blood, grass, eggs, meat, gravy, tomato sauce). Nonlimiting examples of commercially available proteases that can be used include Alcalase™, Alcalase Ultra™, Everlase™, Liquanase™, Liquanase Ultra™, Polarzyme™, Savinase , and Savinase Ultra (available from Novozymes), and Purafast , Purafect® OX, Purafect® L, Purafect® Prime L, Purafect® OX L, Properase® L, and Excellase™ (available from Genencor International, Inc.). Lipases made be used in detergent formulations or stain treatments in which it is desired to remove oily residues or stains (e.g., oil, greasy food stains, oily personal product stains). If a lipase is used, it can be of bacterial or fungal origin, or chemically modified lipases may be used. Nonlimiting examples of commercially available lipases include Lipolase™, Lipoclean™ and Lipex™ (available from Novozymes A/S, Denmark). Amylases may be used in detergents or stain treatments in which it is desired to remove starchy soils. If an amylase is included in a surfactant composition, an a-amylase or an engineered mutant amylase may be used. Nonlimiting examples of commercially available amylases include Duramyl™, Termamyl™, Termamyl Ultra™, Stainzyme™, Stainzyme Plus™ (available from Novozymes), and Rapidase™, Purastar™, Powerase™, (available from

Genencor Int'l, Inc.). Cellulases may be used in detergents or stain treatments in which it is desired to clean general soils such as dirt and mud. If a cellulase is used, it may be bacterial or fungal in origin. Chemically modified or engineered mutant cellulases may be used. In some casese, alkaline or neutral cellulases are used to add color performance properties to a laundry detergent. Nonlimiting examples of commercially available cellulases include Celluclean™, Endolase™, Celluzyme™ and Carezyme™ (available from Novozymes), Clazinase™ and Puradax™ HA and Puradax™ EG (available from Genencor Int'l, Inc.), and KAC-500™ or KAC-700™ (available from Kao Corp., Tokyo, Japan). If a peroxidase or oxidase is included in a surfactant composition, it may be derived from plant, bacteria or fungi. In some variations, chemically modified or engineered mutant peroxidase or oxidases are used. Nonlimiting examples of commercially available peroxidases include Guardzyme™ (available from

Novozymes). A pectinase may be used in formulations in which it is desired to remove fruit or fruit juice residues. Nonlimiting examples of commercially available pectinases include Pectiwash™ and XPect™ (available from Novozymes). Mannanases may be used in detergent or stain treatment formulations in which it is desired to remove gum based residues.

Nonlimiting examples of commercially available mannanases are Mannaway™ (available from Novozymes) and Mannastar 375™ (available from Genencor Int'l, Inc.).

[0325] In cleaning formulations that comprise one or more enzymes, one or more enzyme stabilizers may also be included. Any enzyme stabilizer or combination of enzyme stabilizers known in the art may be used. For example, magnesium ions soluble in water (e.g., magnesium sulfate), calcium ions solubile in water (e.g., calcium chloride), polyols (propylene glycol or glycerol), a sugar or an alcohol derived from a sugar, lactic acids, boric acid, borates, or any combination of two or more of the foregoing.

[0326] If an enzyme is included in a surfactant composition as described herein (e.g., in a cleaning composition such as a laundry detergent), it may be present in any effective amount. For example, an enzyme may be present at about 0.00001 wt% or higher, about 0.0001 wt% or higher, 0.001 wt% or higher, 0.01 wt% or higher, 0.01 wt% or higher, 0.1 wt% or higher, 0.5 wt% or higher, or 1 wt% or higher. In some variations, one or more enzymes are present in a cleaning composition comprising one or more Diels- Alder adducts as described herein in an amount of about 0.00001 wt% to about 5 wt% (e.g., about 0.00001wt% to about 0.0001wt%, about 0.000 lwt% to about 0.00 lwt%, about 0.0001 wt% to about 0.01wt%, about 0.0001 wt% to about 0.1 wt%, about 0.0001 wt% to about 1 wt%, about 0.0001 wt% to about 5wt%, about 0.001 wt% to about 0.01 wt%, about 0.001 wt% to about 0.1 wt%, about 0.001 wt% to about 1 wt%, about 0.001 wt% to about 5wt%, about 0.01 wt% to about 0.1 wt%, about 0.01 wt% to about 1 wt%, about 0.01 wt% to about 5 wt%, about 0.1 wt% to about 1 wt%, or about 0.1 wt% to about 5wt%).

[0327] In some cases, cleaning compositions (e.g., laundry detergents, dishwasher detergents, stain treatment formulations, or industrial cleaning compositions) may comprise one or more builders. Any builder or combination of builders known in the art may be used. In general, builders may function to reduce the concentration of polyvalent cations in wash water that contribute to hard water, such as calcium and magnesium. In general, builders can function by ion exchange, sequestration or precipitation of the cations. Nonlimiting examples of builders include addititives capable of sequestering calcium or magnesium, calcium ion-exchange materials, magnesium ion-exchange materials, and materials to cause precipation of magnesium or calcium. In some formulations, phosphorus-free builders are used. In some variations, citrate builders are used, such as citric acid or water soluble salts of citric acid (e.g., sodium citrate). In some variations, polycarboxylates or aminocarboxylates are used. In some variations, builders derived from succinic acid are used, such as C5-C20 alkyl or alkenyl succinic acids and salts thereof, or ethylene diamine disuccinic acid or salts thereof, ethylene diamine tetracetic acid or slats therof, or diethylene triamine pentaacetic acid or salts thereof.

[0328] In some variations, a polycarboxylate Diels-Alder adduct or a salt thereof (e.g., a sodium salt) or an aminocarboxylate Diels-Alder adduct or a salt thereof as described herein may function as a builder. [0329] If one or more builders are used in a cleaning composition, such one or more builders may be present in any suitable amount, e.g., about 0.5wt% to about 60wt%, based on the total weight of the composition. For example, a composition may contain one or more builders at about 0.5wt% to about 50wt%, about lwt% to about 60wt%, about 1 wt% to about 50wt%, about 1 wt% to about 40wt%, about 1 wt% to about 30wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 10wt%, about 0.5 wt% to about 5 wt%, or about 1 wt% to about 5 wt%.

[0330] In some variations, cleaning compositions may comprise one or more chelating agents (e.g., organic sequestering agents), e.g., one or more copper, iron or manganese chelating agents. Any chelating agent or combination of chelating agents known to be capable of removing of removing ions such as copper iron or manganese by forming a soluble chelate can be used. In some variations, a phosphorus-free chelating agent is used. For example, amino carboxylates (e.g., ethylene diamine disuccinate), or methyl glycine diacetic acid or salts thereof may be used. Certain compositions may comprise nitroloacetic acid, ethylene diamine tetraacetic acid, phosphonates, citrates (e.g., sodium citrate), monosuccinates (e.g., sodium tartrate monosuccinate), disuccinates (e.g., sodium tartrate disuccinate), or mixtures of two or more of the foregoing. In some variations, an aminocarboxylate Diels-Alder adduct as described herein may be used as a chelating agent. One or more chelating agents, if present, may be present in an amount of about 0.001 wt% to about 10 wt%, based on a total weight of the composition. For example, a composition may contain one or more chelating agents at about 0.005 wt% to about 10 wt%, about 0.005 wt% to about 5 wt%, about 0.005 wt% to about 1 wt%, about 0.005 wt% to about 0.1 wt%, about 0.005 wt%, to about 0.05 wt%, about 0.001 wt% to about 0.1 wt%, about 0.01 wt% to about 0.1 wt%, about 0.001 wt%, about 0.005 wt%, about 0.01 wt%, about 0.05 wt%, about 0.1 wt%, about 0.5wt%, about 1 wt%, about 5 wt%, or about 10wt%.

[0331] In some variations, a cleaning composition comprises one or more hydrotropes to solubilize one or more components of a composition or to improve physical and/or chemical stability of the composition. Any hydrotrope or combination of hydrotropes can be used. In some variations, one or more sulfonated hydrotropes are used. One or more hydrotropes can be present in any suitable amount, e.g., about 0.01wt% to about 20wt%, based on the total weight of the composition. For example, a composition may contain one or more hydrotropes at about 0.01 wt% to about 15 wt%, about 0.01 wt% to about 10 wt%, about 0.01 wt% to about 5 wt%, about 0.05 wt% to about 1 wt%, about 0.05 wt%, to about 5 wt%, about 0.05 wt% to about 10 wt%, about 0.1 wt% to about 1 wt%, about 0.01 wt%, about 0.1 wt%, about 1 wt%, about 2 wt%, about 5 wt%, about 10wt%, about 12 wt%, about 15 wt%, or about 20wt%.

[0332] In some variations, one or more rheology or viscosity modifiers are included in a cleaning composition. Any rheology or viscosity modifier known in the art may be used in any effective amount. In some cases, a rheology modifier is used that decreases viscosity of a formulation when shear is applied. Nonlimiting examples of rheology modifiers include polyacrylates, polysaccharides, and polycarbxylate polymers used with a solvent (e.g., an alkylene glycol). One or more rheology modifiers, if used, may be present at about 0.1 wt% to about 20 wt%, based on the total weight of the composition. For example, a composition may contain one or more rheology modifiers at about 0.1 wt% to about 15 wt%, about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 5 wt%, about 0.5 wt% to about 1 wt%, about 0.5 wt%, to about 5 wt%, about 0.5 wt% to about 10 wt%, about 1 wt% to about 5 wt%, about 0.1 wt%, about 1 wt%, about 2 wt%, about 5 wt%, about 8 wt%, about 10wt%, about 12 wt%, about 15 wt%, or about 20wt%. In some variations, a Diels- Alder as described herein (e.g., a

polycarboxylate) may be used as a rheology modifier.

[0333] In some variations, a cleaning composition includes one or more solvents. In other variations, a cleaning composition does not include a solvent. Nonlimiting examples of suitable solvents include water, organic solvents, hydrocarbons, polyols (e.g., diols such as ethylene glycol or propylene glycol, or 1 ,2-propanediol, or polyols containing 3 or more hydroxyl groups such as glycerol), glycol ethers, ethers of glycerol, siloxanes, silicones, primary alcohols and secondary alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, isohexanol, and suitable saturated fatty alcohols (e.g., isostearyl alcohol) or unsaturated fatty alcohols). In some variations, a Diels- Alder adduct that is an alchol, polyol (e.g., a diol), monoester or diester as described herein is used as a solvent for a cleaning composition, either alone or in combination with one or more additional solvents. In those compositions in which one or more solvents is used, a solvent may comprise about 0.1 wt% to about 99.9wt% of a cleaning composition (e.g., about 1 wt% to about 99 wt%, about 1 wt% to about 90wt%, about 1 wt% to about 80wt%, about 1 wt%, to about 70 wt%, about 1 wt% to about 60 wt%, about 1 wt% to about 50wt%, about 1 wt%, about 5 wt%, about 10wt%, about 20 wt%, about 30wt%, about 40wt%, about 50wt%, about 60 wt%, about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, about 98 wt%, or about 99 wt%).

[0334] In some cleaning compositions (e.g., laundry detergents or stain treatment formulations), one or more bleaching agents is included. A bleaching agent may oxidize (or in some cases reduce) a component of a stain such that it becomes more soluble and removeable, or by changing the color of the stain such that it is no longer as apparent. Nonlimiting examples of bleaching agents include peracids (e.g. percarboxylic acids and salts thereof, percarbonic acids and salts thereof, perimidic acids and salts therof, peroxymonosulfuric acids and salts thereof), peroxides (e.g., any source of hydrogen peroxide such a perborates and percarbonates), metal bleach catalyst, and photobleaches. Peracids may be preformed or formed in situ using an activator. In some cases, a bleach activator is used that comprises a peracid precursor.

Nonlimiting examples of bleach activators include tetraacetylethylenediamme (which generates two equivalents of peracid when reacted with hydrogen peroxide) and

nonanoyloxybenzenesulfonate (which generates one equivalent of peracid when reacted with hydrogen peroxide). One nonlimiting example of a preformed peracid is

phthalimidoperoxycaproic acid. In some cases, one or more metal bleach catalysts are used that react with a source of oxygen to make an oxidizing agent that functions in a formulation as a bleaching agent. Nonlimiting examples of metal bleach catalysts include transition metal compounds (e.g., Fe, Co, Mn, or Cu) with chelating ligands. Photobleaches generate an oxidizing species upon exposure to light (e.g., sunlight) in air. Nonlimiting examples of photobleaches include metal phthalocyanines (sulfonated zinc phthalocynanine, sulfonated aluminium phthalocyanine), xanthene dyes, EosinY, Phoxine B, Rose Bengal, and mixtures of any two or more or the foregoing. In some cases, one or more photoinitiators are used with a photbleach.

[0335] In some cleaning compositions, one or more pearlescent agents are included.

Any one of or any combination of pearlescent agents known in the art may be used. Suitable pearlescent agents may be organic or inorganic. Nonlimiting examples of organic pearlescent agents include monoesters or diesters of alkylene glycols, propylene glycol, diethylene glycol, dipropylene glycol, methylene glycol or tetraethylene glycol with saturated or unsaturated fatty acids having about 6 to 22 carbons (e.g., about 12 to 18 carbons) such as caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic aclid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid, erucic acid, and mixtures of two or more of the foregoing. In certain variations, a Diels-Alder adduct as described herein may function as pearlescent agents or as a component of a pearlescent agent (e.g., polyols such as diols, or monoesters or diesters of diols) Nonlimiting examples of inorganic pearlescent agents include mica and coated micas (e.g., silica coated mica or metal oxide coated mica). Inorganic pearlescent agents may be formulated as slurries, suspensions, or powders.

[0336] In some variations, one or more fragrances are included in a cleaning

composition. The term "fragrances" is meant to include any individual ingredient, perfume or combination of ingredients or perfumes that imparts a desired odor to a composition. Fragrances may be incorporated in any suitable form, e.g., as raw ingredients, premixed, or encapsulated by any encapsulant as known in the art.

[0337] One or more fabric conditioners are included in certain variations of laundry detergent compositions or laundry aids. A fabric conditioner is any substance that can soften fabrics, protect color, resist wrinkling, protect color, and the like, when present in an effective amount. Nonlimiting examples of fabric conditioners include cationic surfactants, polyolefms, latexes, fatty acids, silicones, polyurethanes, and combinations thereof. In certain variations, a cationic Diels- Alder adduct surfactant as described herein functions as a fabric conditioner in a laundry detergent or laundry aid. In certain variations, a Diels-Alder adduct alcohol or acid as described herein functions as a fabric conditioner in a laundry detergent or laundry aid. Fabric conditioners, if present, may be incorporated in any effective amount in a laundry composition. For example, a fabric conditioner may be present at about 0.1 wt% to about 30 wt%, e.g., about 0.1 wt% to about 20wt%, about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt%, about 0.5wt%, about 1 wt%, about 5 wt%, about 10wt%, about 15 wt%, about 20 wt%, about 25wt%, or about 30 wt%.

[0338] Some laundry detergents or laundry aids comprise one or more dye transfer inhibitors in an effective amount. Dye transfer inhibitors are capable of complexing, absorbing, or otherwise preventing dyes washed out of dyed fabrics from coloring other fabrics.

[0339] In some cases, cleaning compositions as described herein exhibit disinfecting and/or sanitizing properties as well as beneficial and useful cleaning properties.

[0340] In some variations, the surfactants described herein are employed in personal care products or emollients for use in skin care, hair care, shaving creams, cosmetics and the like. For example, Diels-Alder adducts as described herein that are alcohols (e.g., compound J-7-IA or J-7-IB), diols (e.g., compound J-7-ΓΧ), monoesters (e.g., compound H-IC or H-ID with R being methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, or 2-ethylhexyl) or diesters (e.g., compound H-IIB with R⁴ and R⁴ each being Ci to C₂o hydrocarbyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, or 2-ethylhexyl) may be utilized as personal care products.

[0341] Attributes for surfactants for use personal care applications include slip, lubricity, spreadability on skin and on paper, absorbency, solubility, cushion, gloss, after-feel, color, odor, and viscosity. In some personal care applications (e.g., emollients), it is desired that the substance provide a smooth, silky, non-greasy, non-tacky, powdery feel after application. Light emollients exhibit lower viscosity, high slip, high lubricity, absorb quickly, and spread easily on skin. Heavy emollients provide more cushion to the skin and are more difficult to spread. One or more of the surfactants as described herein may be used alone as emollients, or two or more of the surfactants described herein may be blended for use as emollients. One or more surfactants as described herein may be blended with one or more additional surfactants or ingredients for use as emollients. Optional additives to personal care formulations comprising one or more surfactants as described herein include thickeners, colorants, solvents, rheological modifiers, inorganic powders or other particles, fragrances, stabilizers, oils, waxes, silicones, fatty acids, and fatty alcohols. Advantageously, in some personal care formulations, surfactants as described herein may be useful to replace at least a portion of a silicone-containing component of the formulation.

[0342] In some variations, the surfactants as described herein are prepared as water-in- oil type emulsions for use in personal care products. For example, Diels-Alder adducts as described herein that are alcohols (e.g., compound J-7-IA or J-7-IB or compounds having formula (J-7-IIA) or (J-7-IIB)), polyols such as diols (e.g., compound J-7-IX or compounds having formula (J-7-X)), monoesters (e.g., compound H-IC or H-ID with R being methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, or 2-ethylhexyl) or diesters (e.g., compound H-IIB with R⁴ and R⁴ each being a C1-C20 hydrocarbyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, or 2- ethylhexyl) may be formulated as water-in-oil type emulsions that can be utilized in personal care products.

[0343] Optionally, any one of or any combination of silicone oils (e.g., polysiloxanes), organic or hydrocarbon oils, waxes, colorants, fragrances, flavors (e.g., for lip balm), fatty alcohols, vitamins, stabilizers, antioxidants, preservatives, thickeners, antiseptics, diluents, pH adjuster, chelating agent, sunscreen, buffer, dispersing agent may be added to a personal care formulation. [0344] Nonlimiting examples of oils that may be used in personal care formulations in combination with one or more surfactants as described herein include ester oils, hydrocarbon oils, liquid paraffins, squalane, farnesane, avocado oil, camellia oil, nut oil, corn oil, olive oil, rapeseed oil, sesame oil, wheat germ oil, castor oil, linseed oil, safflower oil, cottonseed oil, soybean oil, peanut oil, tung oil, rice bran oil, triglycerol, glyceryl trioctanoate, cacao oil, jojoba oil and palm oil. Nonlimiting examples of waxes that may be used in personal care formulations in combination with one or more surfactants as described herein include bees wax, candelilla wax, carnauba wax, lanolin, and cane wax. Nonlimiting examples of fatty acids and alcohols that can be used in combination with one or more surfactants as described herein include behenyl alcohol, batyl alcohol, stearyl alcohol, isostearyl alcohol, stearic acid, isostearic acid, and palmitic acid.

[0345] One or more surfactants as described herein may comprise any suitable portion of a personal care formulation, e.g., about 0.001wt% to about 100 wt%, about 0.001wt% to about 90%, about 0.001 wt% to about 80wt%, about 0.001 wt% to about 70wt%, about 0.001 wt% to about 60 wt%, about 0.001 wt% to about 50 wt%, about 0.001 wt% to about 40 wt%, about 0.001 wt% to about 30 wt%, about 0.001 wt% to about 20 wt%, about 0.001 wt%, to about 10 wt%, about 0.001 wt% to about 5 wt%, about 0.001 wt% to about 1 wt%, about 0.001 wt%, about 0.005 wt%, about 0.01 wt%, about 0.05 wt%, about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, about 5 wt%, about 8 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70wt% about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 95 wt%, about 99wt%, or about 100 wt%.

[0346] Certain personal care formulations (e.g., emollients such as facial creams) comprise a Diels-Alder adduct described herein that is an alcohol or a polyol and one or more of the following: squalane, farnesane, isostearyl alcohol, and behenyl alcohol.

[0347] In one example, a Diels-Alder adduct that includes an anhydride moiety is useful as a paper sizing agent, e.g., for cellulose-containing papers. The hydrophilic head of the Diels- Alder adduct may interact with cellulose fibers to provide cohesion, and the hydrophobic tail originating from the conjugated terpene may provide printability and water resistance. The hydrocarbon terpene used in such applications may in some paper sizing applications be β- farnesene or a-farnesene. However, other conjugated hydrocarbon terpenes described herein or otherwise known may be used. Any of the anhydride-containing adducts described herein may be used for paper sizing applications, e.g., maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides.

[0348] In some variations, the surfactant compounds described herein are useful as solvents. They may be useful as solvents in a variety of formulations for a variety of applications (e.g., personal care products, industrial solvents, cleaning products, lubricants, agricultural products, coatings, and the like). To evaluate suitability as solvents in particular applications, Hansen solubility parameters may be used. Hansen solubility parameters were calculated for a number of theoretical and synthesized solvents derived from myrcene or farnesene using HSPiP software program, available at .h os^ The Y-MB algorithm was used to calculate estimated HSP parameters 5D, δΡ and δΗ for Diels-Alder adducts that may be derived from β -farnesene or myrcene as described herein, and are shown in Table 4. Hansen solubility parameters were also calculated for a number of commercial solvents (Table 5). As used below, glu indicates a glucose unit.

[0349] In some variations, a Diels-Alder adduct or derivative thereof as described herein has utility as an emollient and as a UV absorber (e.g., for a light stabilizing compound or sunscreen applications). One illustrative and nonlimiting example of a compound that may exhibit properties as an emollient and be capable of absorbing UV light in a useful wavelength range is a Diels-Alder adduct between β -farnesene and a quinone (preparation provided in Example 20). In some variations, a Diels-Alder adduct between β-farnesene and a quinone may be oxidized to increase the degree of conjugation, thereby tuning the UV absorption to the red.

Table 4. 6D, δΡ and δΗ for Myrcene and β-Farnesene Derived Solvents

Page 132 of 167 Table 5: 6D, δΡ and δΗ for Commericial Solvents

[0350] The solvents described herein can be compared with existing solvents and used to replace existing solvents in formulations, or in combination with existing solvents in

formulations. One method that can be used to identify potential applications for the solvents described herein (e.g., those identified in Table 4) is to plot δΗ vs. δΡ for hydrocarbon terpene derived solvent described herein as well as existing solvents, and identify existing solvents with having similar (δΗ, δΡ).

[0351] While the compounds, compositions and methods have been described with respect to a limited number of embodiments, the specific features of certain embodiments should not be attributed to other embodiments described herein. No single embodiment is

representative of all aspects of the compositions or methods. In some embodiments, the compositions or methods may include numerous compounds or steps not mentioned herein. In other embodiments, the compositions or methods do not include, or are substantially free of, any compounds or steps not enumerated herein. Variations and modifications from the described embodiments exist.

EXAMPLES

[0352] For the following Examples, β-farnesene refers to trans- -farnesene. Unless otherwise specified, β-farnesene is manufactured using genetically modified organisms by Amyris, Inc., and has been distilled prior to use to result in a purity of >97%, and includes lOOppm 4-tert-butylcatechol (TBC) as stabilizer. As used herein, Me refers to a methyl group.

Example 1. Preparation of 5-(4,8-Dimethylnona-3,7-dienyl)cyclohex-4-enecarboxylic acid methyl ester (la) and 4-(4,8-Dimethylnona-3,7-dienyl)cyclohex-3-enecarboxylic acid methyl ester (lb).

la lb

[0353] A 3 L round-bottomed flask equipped with a magnetic stirrer, heating mantle and reflux condenser was charged with 704 g (3.44 mol) of β-farnesene (>97% pure, Amyris, Inc.), 342 mL (326 g, 3.79 mol) of methyl acrylate and 1.0 g (3.1 mmol) of Znl. Toluene (200 mL) was added and the stirring mixture was heated to 80-95 °C. After 14 hours the reaction was allowed to cool to ambient temperature and filtered through a 9.5 cm X 5.5 cm column of neutral alumina using 300 mL of hexane as a rinsing solvent. The bulk of the two solvents were removed under reduced pressure to afford 1025 g of crude isomeric ester mixture la, lb as a pale yellow oil. The product was characterized by the following NMR data: 1H NMR (CDCI₃): δ 5.39 (s, br, 1H), 5.10 (m, 2H), 3.69 and 3.60 (s, 3H total), 2.45 (m, 1H), 2.27-1.92 (m, 13H), 1.68 (s, 3H), 1.67 (m, 1H), 1.60 (s, 3H) and 1.59 (s, 3H).

Example 2. Preparation of β-Farnesene-Maleic Anhydride Diels Alder Adduct (14)

[0354] Distilled β-farnesene (Amyris, about 1.5 L) was stirred with anhydrous magnesium sulfate (Fisher Scientific, 150 g) for about 15 minutes, and then filtered (5 micron, nylon). The filtrate was stirred for about 30 minutes with basic super I alumina (Sorbent Technologies, Inc., 75 g) and filtered (5 micron, nylon) to give a colorless, highly transparent filtrate which was identified as β-farnesene. A portion of the filtrate (502.7 g, 2.460 mol) was combined with ethyl acetate (obtained from J.T. Baker 9282-03, 2201.8 g) and the resulting solution stirred for 30 minutes at room temperature under nitrogen. To the solution was added maleic anhydride (obtained from Aldrich Chemical, Ml 88, 99.8%, 240.3 g) and the suspension thus obtained was stirred at room temperature under nitrogen for 12 hours to give a solution. The solution was rotary evaporated (31 °C, 50 torr) and a portion (118.06 g) was distilled (0.17 mm Hg, 220 °C) to give a colorless liquid (73.07g). GC-MS: 13.969 min (99.3 area%), 302 (M+, m/z), Karl Fischer titration determination of water (according to ASTM D6304, which is incorporated herein by reference in its entirety): 18 ppm.

Example 3: Preparation of Ethoxylated Alcohol from Diels-Alder Adduct

[0355] An ethoxylated alcohol is prepared from a Diels-Alder adduct between β- farnesene and acrolein accordin to Scheme 28 below.

28-1 28-2

28-3 28-4

SCHEME 28

Preparation of Aldehyde (28-2).

[0356] A 3 L round-bottomed flask equipped with a magnetic stirrer, heating mantle and reflux condenser connected to a nitrogen bubbler was flushed with nitrogen and charged with β- farnesene (785 g, 3.84 mol), Znl₂ (available from Sigma- Aldrich) ( 1.0 g, 3.1 mmol) and toluene (200 mL). The stirring was started and 80 mL of acrolein (available from Sigma-Aldrich) added. The mixture was then heated to a very low reflux and after two hours an additional 177 mL of acrolein were added at such a rate that the ref uxing was controlled. After 24 hours the reaction was allowed to cool to ambient temperature and filtered sequentially through a 9.5 X 5.5 cm column of silica gel and a 3cm x 4cm pad of Celite filter (available from Sigma- Aldrich). The filtrations were washed with 1 L of hexane. The combined filtrates and washings were evaporated under reduced pressure to afford 1014 g of crude product as a very pale yellow oil. The pale yellow oil was characterized as follows: GC/MS, m/z 260 (M⁺); 1H NMR (CDC1₃), δ (9.69, J=1.2 Hz, lH and 9.68, J=1.2 Hz, 1H, ratio 1 :3.8), 5.42 (brs, 1H), 5.10 (dt, J=3.4 and 1.2 Hz, 2H), 2.45 (m 1H), 2.22 (m, 2H), 2.05 (m, 8H), 1.99 (m, 4H), 1.68 (s, 3H), 1.60 (s, 3H), 1.59 (s, 3H).

Preparation of Alcohol (28-3).

[0357] To a 1L round-bottomed flask equipped with a magnetic stirrer were added 58 1 g (0.223 mol) of aldehydes (28-2) and 250 mL of absolute ethanol. The mixture was stirred and 3.09 g (0.0812 mol) of NaBH₄ were added in portions at such a rate that the rate of gas evolution was controlled. One hour after addition of the last portion the reaction was complete. A solution of 0.3% aqueous HCl was carefully added dropwise to destroy the excess NaBH₄ and the bulk of the ethanol removed under reduced pressure. The oily aqueous residue was partitioned between 100 mL of ethyl acetate and 250 mL of H₂0. The layers were separated and the aqueous phase extracted with ethyl acetate (2 times 50 mL). The organic phases were combined washed with saturated NaCl solution (2 times 50 mL), dried (MgS0₄) and the solvent removed under reduced pressure. The residual oil was distilled using a Kugelrohr distillation apparatus to provide 43.4 g (74.2%) of a 1 :3.8 isomer mixture of alcohol (28-3) as a colorless oil: Bp 190°C @ 1.0 mm: GC/MS, m/z 262 (M⁺); 1H NMR (CDC1₃), δ 5.37 (brs, 1H), 5.10 (dt, J=3.4 and 1.2 Hz, 2H), 3.50 (m, 2H), 2.07 (m, 6H), 1.98 (m, 5H),1.82 (m, 1H), 1.73 (m, 1H), 1.68 (s, 3H), 1.60 (s, 6H), 1.26 (m, 1H); ¹³C NMR (CDC1₃), δ 137.7, 136.5, 135.0, 131.2, 124.4, 124.3, 120.7, 119.5, 67.8, 67.7, 39.7, 37.9, 37.7, 36.8, 36.3, 31.4, 28.3, 27.8, 26.8, 26.4, 25.7, 25.3, 24.8, 17.7, 16.0.

Preparation of Alcohol (28-4).

[0358] Alcohol (28-3) (43.0 g, 0.164 mol), 10% Pd/C and ethyl acetate (350 mL) were placed in a IL Parr autoclave and placed under 950 psig of hydrogen. The mixture was rapidly stirred (500 rpm) and heated to 75°C. As the reaction progressed the hydrogen pressure was readjusted to 950 psig. After 36 hr the heating was discontinued and the catalyst removed by vacuum filtration. The ethyl acetate was removed under reduced pressure to afford 43.0 g (97.7%o) of alcohol (28-4) as a colorless oil with isomer ratio as above for alcohol (3): GC/MS, m/z 268 (M⁺); 1H NMR (CDC1₃), δ 3.51 (d, J=6.4 Hz, 2H), 3.42 (d, J=6.4 Hz, 2H), 1.78 (d, J=8.4 Hz), 1.7-1.0 (m, 21H), 0.90 (m, 2H), 0.87, 0.86, 0.85, 0.83 (s, CH₃, total 9H); ^ljC NMR (CDC1₃), δ 68.7, 68.7, 40.7, 40.6, 39.4, 38.4, 38.0, 37.9, 37.8, 37.4, 37.4, 37.3, 37.3, 32.8, 32.7, 29.6, 29.5, 28.9, 28.8, 28.0, 25.8, 25.4, 24.8, 24.4, 24.3.

Preparation of Ethoxylated Alcohol (28-5) (prophetic).

[0359] Alcohol 28-4 will be ethoxylated under standard industrial conditions to produce the ethoxylated alcohol 28-5 as a colorless oil. To achieve ethoxylated alcohol 28-5 having an average value of n=9, nine molar equivalents of ethylene oxide can be used per mole of alcohol 28-4.

Example 4. Preparation of an Ethoxylated Alcohol from a Diels-Alder Adduct (prophetic)

[0360] An ethoxylated alcohol may be prepared from a Diels-Alder adduct between β- farnesene and acrolein according to Scheme 29 below.

n= ca. 9

28-5

SCHEME 29

[0361] Referring to Scheme 29, the aldehyde (28-2) will be prepared as described in

Example 28 above. The aldehyde (28-2) will be reduced with a Ruthenium on carbon catalyst using a hydrocarbon co-solvent in an autoclave at elevated temperature (75 to 100°C) with hydrogen gas at pressures between about 500 to lOOOpsig. The catalyst will be removed by vacuum filtration and the co-solvent evaporated under reduced pressure to produce the alcohol (28-4). The ethoxylated alcohol (28-5) will be produced from alcohol (28-4) as described in Example 28 above.

Example 5. Preparation of (E)-dimethyl 4-(4,8-dimethylnona-3,7-dienyl)cyclohex-4-ene- 1 ,2-dicarboxylate

[0362] A 5 L, 3 neck flask was equipped with a magnetic stir bar, a N₂ inlet, a type-J teflon covered thermocouple, and a reflux condenser. β-Farnesene (900 g, 4.40 mol) and dimethyl maleate (604 mL, 4.63 mol) were added. The mixture was heated to 110°C and stirred overnight. After it was determined by GC/MS and NMR that the reaction had not gone to completion, the mixture was heated to 130°C and stirred overnight, after which time it was complete. The material was pre-adsorbed onto 1.5 kg flash-grade silica by dissolving in CH₂CI₂ (1.5 L) followed by concentration under reduced pressure. The material was then loaded onto a column of flash-grade silica (3 kg) and eluted with: hexanes (4 L), 10% ethyl acetate / hexanes (10 L), 20% ethyl acetate / hexanes (10 L), 30% ethyl acetate / hexanes, 40% ethyl acetate / hexanes. The fractions (2 L) were collected. Those fractions containing the desired compound were collected (10 L - 22 L) and concentrated to provide (E)-dimethyl 4-(4,8-dimethylnona-3,7- dienyl)cyclohex-4-ene-l,2-dicarboxylate (1414 g, 92% yield). FIG. 1 shows a proton NMR spectrum of (E)-dimethyl 4-(4,8-dimethylnona-3,7-dienyl)cyclohex-4-ene-l,2-dicarboxylate.

Example 6: Preparation of dimethyl 4-(4,8-dimethylnonyl)cyclohexane-l,2-dicarboxylate

[0363] To a N₂ flushed carboy (8 L) was added nickel catalyst -65 wt% on

silica/alumina (101 g), heptanes (2 L), (E)-dimethyl 4-(4,8-dimethylnona-3,7-dienyl)cyclohex-4- ene-l,2-dicarboxylate (501 g, 1.44 mol) and further heptanes (1.4 L). This slurry was transferred to the autoclave with additional heptanes (700 mL) then purged twice with N₂ (500 psi). H₂ (500 psi) was added and solution was heated to 80-90°C. Upon reaching temperature, further H₂ was added (1100 psi). Samples were pulled by venting H₂ followed by a N₂ purge. By 1H NMR, the reaction was determined to be complete at 48h. The slurry was discharged from the autoclave. The autoclave was rinsed with heptanes (3 L). The slurry was filtered through ¼" celite in a 2L fritted funnel (M) then chased with further heptanes (4 L). The solution was concentrated under reduced pressure to provide dimethyl 4-(4,8- dimethylnonyl)cyclohexane-l,2-dicarboxylate (498 g, 98% yield). FIG. 2 shows a proton NMR spectrum of dimethyl 4-(4,8-dimethylnonyl)cyclohexane-l,2-dicarboxylate.

Example 7. Preparation of (4-(4,8-dimethylnonyl)cyclohexane-l,2-diyl)dimethanol

[0364] A 22 L, 4 neck flask was equipped with an overhead mechanical stirrer, a N₂ inlet, a type-J teflon covered thermocouple, a reflux condenser, an addition funnel and a water bath. A THF solution of Lithium aluminum hydride (4.0 L, 4.0 mol) was cannulated into the flask. Dimethyl 4-(4,8-dimethylnonyl)cyclohexane-l,2-dicarboxylate (941 g, 2.65 mol) was added to the addition funnel, diluted with heptane (2.8 L) and added to the flask over 50 min. while maintaining a reaction temperature of < 40°C. Following the addition, the water bath was dropped and the reaction was stirred for lh. By TLC, the reaction was determined to be complete (R_f (Dimethyl 4-(4,8-dimethylnonyl)cyclohexane-l,2-dicarboxylate) = 0.70 (30% ethyl acetate/hexanes) vs. R_f(4-(4,8-dimethylnonyl)cyclohexane-l,2-diyl)dimethanol) = 0.10 (30% ethyl acetate/hexanes). The solution was cooled to 5°C. Water (150 mL) was added over 30 min. 15% NaOH (150 mL) was added followed by a further portion of water (450 mL). The solution was stirred for 25 min. Na₂S0₄ (400 g) was added. The slurry was stirred overnight, filtered through celite and concentrated to provide (4-(4,8-dimethylnonyl)cyclohexane-l,2- diyl)dimethanol (784 g, 99% yield). FIG. 3 shows a proton NMR spectrum and FIGS. 4A and

13

4B show C NMR spectra of (4-(4,8-dimethylnonyl)cyclohexane-l,2-diyl)dimethanol.

Example 8. Preparation of a mixture of (E)-3-(4,8-dimethylnona-3,7-dienyl)cyclohex-3- enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7-dienyl)cyclohex-3-enecarbaldehyde

[0365] A 3 L, 4 neck flask was equipped with an overhead mechanical stirrer, a N₂ inlet, a type-J TEFLON® covered thermocouple, a reflux condenser, and an addition funnel. Toluene (200 mL), zinc iodide (7.81 g, 2.45 mmol) and acrolein (50 mL, 711 mmol) were added. The solution was heated to 70°C to initiate the reaction. Acrolein (250 mL 3.55 mol) and zinc iodide (2.84 g, 8.9 mmol) were added to maintain a reaction temperature of 70-80°C. (N.B. When the reaction failed to display an exotherm upon addition of acrolein, the solution was cooled to rt and a further charge of zinc iodide was added. The solution was then warmed to 70°C and addition of acrolein continued). Following the addition, the solution was stirred at reflux overnight. The solution was concentrated to provide the crude material (1078 g) which was pre- adsorbed onto 1.3 kg flash-grade silica by dissolving in CH₂C1₂ (2.0 L) followed by

concentration under reduced pressure. The material was then loaded onto a column of flash- grade silica (3.8 kg) and eluted with: hexanes (6 L), 10% EtOAc / hexanes (10 L), 20% EtOAc / hexanes (20 L). The fractions (2 L) were collected. Those fractions containing the desired compound were collected (12 L - 24 L) and concentrated to provide a mixture of (E)-3-(4,8- dimethylnona-3,7-dienyl)cyclohex-3-enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7- dienyl)cyclohex-3-enecarbaldehyde (859 g, 89%> yield) as shown by 1H NMR in FIG. 5 and by GC/MS in FIGS.6A-6B.

Example 9. Preparation of a mixture of (3-(4,8-dimethylnonyl)cyclohexyl)methanol and (4-(4,8-dimethylnonyl)cyclohexyl)methanol

[0366] To a N₂ flushed 600 mL Parr autoclave was added the mixture of (E)-3-(4,8- dimethylnona-3,7-dienyl)cyclohex-3-enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7- dienyl)cyclohex-3-enecarbaldehyde (50 g, 192 mmol), ruthenium on carbon (6.2 g) and 2- propanol (200 mL). The vessel was pressure-tested with N₂ (900 psi) and purged twice with N₂ (600 psi). H₂ (600 psi) was added and the slurry was heated to 75°C. H₂ (700 psi) was added and maintained for 48h. By 1H NMR, it was determined that the reaction had gone to

completion. The slurry was filtered through ¼" celite in a 200 mL fritted funnel (M) then chased with further 2-propanol (100 mL). The solution was concentrated under reduced pressure to provide a mixture of (3-(4,8-dimethylnonyl)cyclohexyl)methanol and (4-(4,8- dimethylnonyl)cyclohexyl)methanol (52 g, 100% yield) as shown by proton NMR in FIG. 7.

Examples 10-12: Preparation of ethoxylated alcohols

SCHEME 35

[0367] A mixture of (3-(4,8-dimethylnonyl)cyclohexyl)methanol and (4-(4,8- dimethylnonyl)cyclohexyl)methanol as prepared in Example 9 was ethoxylated according to Scheme 35 using standard industrial ethoxylation methods, where n molar equivalents ethylene oxide) was used per mol mixture (3-(4,8-dimethylnonyl)cyclohexyl)methanol and (4-(4,8- dimethylnonyl)cyclohexyl)methanol, where n represents the average number of glycol units in the resulting ethoxylated alcohol. Thus, 5 molar equivalents of ethylene oxide per mol of the mixture of (3-(4,8-dimethylnonyl)cyclohexyl)methanol and (4-(4,8- dimethylnonyl)cyclohexyl)methanol as prepared in Example 9 was used for n=5, 10 molar equivalents of ethylene oxide per mol of the mixture as prepared in Example 9 was used for n=10, and 15 molar equivalents of ethylene oxide per mol of the mixture as prepared in Example 9 was used for n=15. Table 35 shows the resulting ethoxylated alcohols and a calculated HLB value for each ethoxylated alcohol.

[0368] Example 10 was an off-white semi-solid. 1H NMR are shown in FIGS. 8A-8C, and are consistent with the structures shown in Table 35, with n approximately equal to 5 (average number of glycol units). The 1H NMR showed trace amounts of solvents were present (0.7% dichloromethane and 1.0% toluene). FIGS. 8D-8F show ¹³C NMR spectra that are consistent with the structures shown in Table 35. [0369] Example 11 was an off-white semi-solid. 1H NMR spectra are shown in FIGS.

9A-9C, and are consistent with the structures shown in Table 35, with n approximately equal to 10 (average number of glycol units). The 1H NMR showed the presence of trace amounts of solvent (toluene, 0.3%). FIGS. 9D-9F show ¹³C NMR spectra that are consistent with the structures shown in Table 35.

[0370] Example 12 was an off-white semi-solid. 1H NMR spectra are shown in FIGS. lOA-lOC, and are consistent with the structures shown in Table 35, with n approximately equal to 15 (average number of glycol units). The 1H NMR showed the presence of trace amounts of solvent (toluene, 0.3%). FIGS. 10D-10F show ¹³C NMR spectra that are consistent with the structures shown in Table 35.

TABLE 35

12 14.2

Mixture of l-(4,8-dimethylnonyl)cyclohexane -3- methyl-pentadecaethylene glycol and l-(4,8- dimethylnonyl)cyclohexane-4-methyl- pentadecaethylene glycol

Examples 13-15: Preparation of ethoxylated diols

n=5, 10 ard 15

SCHEME 38

[0371] (4-(4,8-dimethylnonyl)cyclohexane-l,2-diyl)dimethanol as prepared in Example

7 was ethoxylated according to Scheme 38 using standard industrial ethoxylation methods, where 2n molar equivalents ethylene oxide) were used per mol (4-(4,8- dimethylnonyl)cyclohexane-l,2-diyl)dimethanol), where n represents the average number of glycol units in the resulting ethoxylated alcohol. Thus, 10 molar equivalents of ethylene oxide per mol of (4-(4,8-dimethylnonyl)cyclohexane-l,2-diyl)dimethanol as prepared in Example 7 was used for n=5; 20 molar equivalents of ethylene oxide per mol of the compound as prepared in Example 7 was used for n=10; and 30 molar equivalents of ethylene oxide per mol of the compound as prepared in Example 7 was used for n=15. Table 38 shows the resulting ethoxylated alcohols and a calculated HLB value for each ethoxylated alcohol.

[0372] Ethoxylation for Example 13 was carried out as follows. A 20L Parr reactor was rinsed with toluene (2L), and purged with nitrogen by pressurizing to 200 psi and venting 2-3 times. This purge was also used to check that all of the fittings on the apparatus were sealed and that no drop in pressure was observed after 1 hour. The vessel was then charged with potassium hydroxide (7.04g, 0.126 mol, 0.075 eq), diol SM2 (500g, 1.675 mol) and toluene (2L), then sealed and stirred. The vessel was purged one last time with nitrogen (up to -100 psi) and vented before proceeding. A 5L round bottom flask— equipped with a dry-ice condenser (passive N₂ flow to top of condenser)— was charged with toluene (2L) and cooled to -78°C with dry-ice/heptanes. The ethylene oxide cylinder was connected to a pressurizing N₂ line on the gas take-off side, and pressurized to 50°C. The liquid take-off side was connected to the metering valve (needle valve), then placed on a balance and tared. All likely places for gas to escape were checked with a handheld monitor for ethylene oxide and secured if necessary. Ethylene oxide (738 g, 16.75 mol) was then bubbled into the cold toluene at a feed rate of ~2g/sec. The ethylene oxide solution temperature rose to slightly above -60°C. While the ethylene oxide was being metered into the cold solvent, the Parr reactor was heated to 120°C. Once the ethylene oxide transfer into the cold solvent was complete, the heads of a prep HPLC pump (Hitachi Prep36) were covered with a bag of dry ice to cool the heads and prevent cavitation. The pump was primed with pure toluene, and then used to meter the cold ethylene oxide solution into the Parr reactor (already at 8psi from heating the toluene solution to 120°C). The feed rate was nominally ~27 mL/min (according to the pump display) but the solution required 2.5 hours to complete which equates to ~8 mL/min (most likely due to partial cavitation in the pump heads). The pressure during this time rose as high as 60 psi. The reaction mixture was stirred at 120°C for 2 hours, then cooled to room temperature and stirred overnight. The reaction mixture was drained out of the reactor, and the reactor was rinsed with 2L toluene. The light brown solution was concentrated on a rotary evaporator to give 1,233 g amber oil

(yield=99%). Ethoxylation of Examples 10-12, 14 and 15 were carried out in a similar manner. For Examples 10-12, 14 and 15, the product froze (at least partially) on standing to give an off- white semi-solid (melting points <50°C). For Example 13, no solid was observed at room temperature.

[0373] Example 13 was an amber oil. 1H NMR are shown in FIGS. 1 lA-11C, and are consistent with the structure shown in Table 38, with n approximately equal to 5 (average number of glycol units). The 1H NMR showed trace amounts of solvent was present (<0.1% toluene). FIGS. 1 lD-1 IF show 13 C NMR spectra that are consistent with the structure shown in Table 38.

[0374] Example 14 was a hazy amber oil. 1H NMR spectra are shown in FIGS. 12A-

12C, and are consistent with the structure shown in Table 38, with n approximately equal to 9.2 (average number of glycol units). The 1H NMR showed the presence of trace amounts of solvent (toluene, 0.4%). FIGS. 12D-12F show C NMR spectra that are consistent with the structure shown in Table 38.

[0375] Example 15 was an off-white semi-solid. 1H NMR spectra are shown in FIGS.

13A-13C, and are consistent with the structure shown in Table 38, with n approximately equal to 15 (average number of glycol units). The 1H NMR showed the presence of trace amounts of solvent (toluene, <0.1%). FIGS. 13D-13F show ¹³C NMR spectra that are consistent with the structures shown in Table 38.

TABLE 38

[0376] Surfactant properties of Examples 10-15 are compared to a commercially available nonionic surfactant, NP-9 (nonylphenol + 9 EO), as a Comparative Example.

Properties measured include Cloud Point (a predictor of temperature for optimum surface activity of surfactants), cmc (critical micelle concentration, ppm), surface tension (measured at 0.01% in aqueous solution, mN/m), interfacial tension (0.1% in aqueous solution against mineral oil), interfacial tension (0.1 % in aqueous solution against C8-C10 triglyceride), and Ross Miles foam.

Cloud point

[0377] Cloud points of the surfactants of Examples 10-15 at 0.1%> in distilled water were measured. Results are shown in Table 39. Cloud points are measured in a standard manner, e.g., by heating the solution to point of clarity, and allowed to cool slowly, and the temperature at which turbidity is first observed upon cooling is recorded as the cloud point.

Critical Micelle Concentration (cmc)

[0378] Critical micelle concentration was measured using a Kruess model K100MK2 tensiometer. Thirteen different solutions of each of the surfactants in distilled water are -3 3

prepared at concentrations ranging from 10^" ppm to 10 ppm. Using the tensiometer, curves of log (surfactant concentration in ppm) vs. surface tension (mN/m) were generated. Log(surface tension) decreases with increasing surfactant concentration over a transition region, and log(surface tension) reaches a plateau at high surfactant concentration. The cmc was determined as the intersection between a line drawn through data points in the transition region, and a line drawn through data points in the plateau region at high surfactant concentration. Surface tension vs. Iogl0(surfactant concentration) are shown in FIGURES 14A, 14B, 14C, and 14D for the surfactants of Example 12, Example 13, Example 14, and Example 15, respectively. As illustrated in FIGURE 14 A, the cmc for the surfactant of Example 12 is about 7 ppm. As illustrated in FIGURE 14B, the cmc for the surfactant of Example 13 is about 2 ppm. As illustrated in FIGURE 14C, the cmc for the surfactant of Example 14 is about 8 ppm. As illustrated in FIGURE 14D, the cmc for the surfactant of Example 15 is about 17 ppm. Results are shown in Table 39.

[0379] The surface tension was determined from the data obtained from the cmc determination described above using the Kruess tensiometer and the Wilhelmy plate attachment. The surface tension at 0.01% was interpolated from the curve (which was in the plateau region). Results are shown in Table 39.

[0380] Interfacial tension of the surfactants of Examples 10-15 at 0.1% in water against mineral oil and against C8-C10 triglycerides (Lipo GC triglycerides, available from Lipo Chemicals, Inc., Paterson, NJ) were measured using the Kruess K100MK2 tensiometer and the du Nouy ring, essentially following ASTM D1331 "Standard Test Methods for Surface and Interfacial Tension of Solutions of Surface- Active Agents," which is incorporated herein by reference in its entirety. Results are shown in Table 39.

[0381] Foam at 25°C was evaluated by the Ross Miles Method (ASTM Dl 173,

"Standard Test Method for Foaming Properties of Surface- Active Agents," which is

incorporated herein by reference in its entirety). Solutions of the surfactants of Examples 10-15 at 0.1% in distilled water were prepared. Foam heights (mm) were evaluated immediately after foam preparation, and after 5 minutes. Results are shown in Table 39.

Table 39. Characterization of surfactants of Examples 10-15 Surfactant HLB Cloud CMC Surface Interfacial Interfacial Ross Ross

calc. point (ppm) tension tension tension vs. Miles Miles

(°C) (mN/m) (mN/m) C8-C10 foam foam

vs. triglycerides height height mineral (mm) (mm) 5 oil initial min.

Ex. 10 9.0 <25 Note 2 Note 2 Note 3 Note 3 27 18

Ex. 1 1 12.4 Note 1 15 28.9 4.7 3.1-3.9 est 6 0

Ex. 12 14.2 81 11 29.2 4.3 5.4 78 60

Ex. 13 12.2 98 3 33.8 3.9 4.4 150 135

Ex. 14 14.8 >100 4 36.8 6.2 4.8 150 120

Ex. 15 16.5 >100 17 42.2 10.1 7 135 105

Comparative Example

NP-9 12.9 54 66 31.1 2.3 2.9 102 90

Note 6 Note 7 Note 8 Note 4 Note 5

Literature Values for NEODOL™ Surfactants (Note 8)

NEODOL™ 91-6 12.5 52 250 33 8 — 110 30

C9-C1 1, 6 EO Note 9 Note 9

NEODOL™ 91-8 14 80 270 37 1 1 — 160 30

C9-C1 1, 8 EO Note 9 Note 9

NEODOL™ 23-5 10.7 <25 7 27 — — - —

C12-C13, 5 EO

NEODOL™ 23- 12 43 17 28 5 — 80 20

6.5 Note 9 Note 9

C12-C13, 6.5 EO

NEODOL™ 25-7 12.3 50 9 30 7 70 10

C12-C15, 7 EO Note 9 Note 9

NEODOL™ 25-9 13.1 74 18 31 8 120 10

C12-C15, 9 EO Note 9 Note 9

NEODOL™ 25- 14.4 78 18 34 10 140 10

12 Note 9 Note 9

C12-C15, 12 EO

NEODOL™ 45-7 1 1.6 45 4 29 — — 90 80

C14-C15, 7 EO Note 9 Note 9

NEODOL™ 45- 14.4 80 7 36 — — 130 70

13 Note 9 Note 9

C14-C15, 13 EO

Note 1. Sample was cloudy in water and sample appearance did not change with temperature

Note 2. Sample was not sufficiently soluble to allow measurement.

Note 3. Lamella broke before meaningful data was obtained.

Note 4. Literature value is 4 mN/m. See, e.g. , Rosen, Milton J.; Dahanayake, Manilal (2000). Industrial Utilization of Surfactants - Principles and Practice. AOCS Press.

Note 5. Literature value is 105mm (initial) and 90mm (5 min). See, e.g. , Technical Datasheet for TERGITOL™ NP-9 Surfactant, available at http://www.dow.com.

Note 6. Literature value is 54°C. See, e.g., Technical Datasheet for TERGITOL™ NP-9 Surfactant, available at http://www.dow.com.

Note 7. Literature value is 60 ppm. See, e.g., See, e.g., Technical Datasheet for TERGITOL™ NP-9 Surfactant, available at ίχ¾ !:¾>ν .^

Note 8. Data for NEODOL™ surfactants are from Shell product literature, available at bttp://w¾r . sb¾13.c o Interfacial tension values are from Rosen, Milton J.; Dahanayake, Manilal (2000). Industrial Utilization of Surfactants - Principles and Practice. AOCS Press

Note 9. Ross Miles foam measured at 0.1%, 50°C

Emulsification

[0382] Emulsification with various oil substances was evaluated for the surfactants of

Examples 10-15 and Comparative Examples (NP-9, PEG 400 Dioleate, PEG 600 Dioleate, Sorbitan Oleate + 5 EO, Sorbitan Oleate + 20 EO, Castor Oil + 25 EO, Castor Oil + 40 EO). The oils were selected to represent certain commercially important products in the agricultural, personal care, and cleaning products applications. Mineral spirits, xylene, and soy methyl ester are used in emulsifiable concentrates in agricultural products; mineral oil, cetyl alcohol, C8-C10 triglycerides, myristyl myristate, and C12-C15 benzoates are common in personal care products; mineral spirits, pine oil and d-limonene are used in household and industrial cleaning products.

[0383] Emulsification was evaluated by first preparing emulsions containing 10% oil and 10% surfactants in water. The emulsions were formed by mixing the components with a Tekmar Ultra Turrax mixer, and allowing the resulting mixture to stand for 24 hours, and inspected for separation after 24 hours. If the first emulsion made with 10% surfactant was stable after 24 hours, a second mixture was made in which the amount of surfactant was 5% and the amount of oil remained at 10%, and the second mixture was allowed to stand for 24 hours, and inspected for separation after 24 hours. If the second emulsion made with 5% surfactant was stable after 24 hours, a third mixture was made in which the amount of surfactant used was 2.5% and the amount of oil remained at 10%, and the third mixture was allowed to stand for 24 hours, and inspected for separation after 24 hours. Cetyl alcohol emulsions were pastes in water when 10%) cetyl alcohol was used, so these mixtures were prepared starting at 5% cetyl alcohol and 5% surfactant. Results are shown in Table 40 and in Table 41. The percentage values in Table 40 and in Table 41 represent the level of surfactant at which the emulsion had separated after 24 hours. That is, a value of 10% in Table 40 or Table 41 indicates the emulsion formed with 10% surfactant and 10% oil was unstable after 24h; 5% indicates the emulsion formed with 10% surfactant and 10% oil was stable after 24h, but an emulsion formed with 5% surfactant and 10% oil in water was unstable after 24h; 2.5% indicates the emulsions formed with 10% surfactant and 10% oil, and 5% surfactant and 10% oil were stable after 24h, but an emulsion formed with 2.5% surfactant and 10% oil was unstable after 24h; and <2.5% indicates that emulsions formed with 10% surfactant and 10% oil, 5% surfactant and 10% oil, and 2.5% surfactant and 10% oil were stable after 24h.

[0384] Table 40 shows emulsions formed with surfactants of Examples 10-15 herein and oils chosen to represent commercially important products in agricultural, personal care and cleaning products industries, using nonylphenol-9 (NP-9) as a Comparative Example. The oils ranged from nonpolar hydrocarbons to esters to more polar alcohols. Mineral spirits, xylene and soy methyl ester may be used in emulsifiable concentrates in agricultural products; mineral oil, cetyl alcohol and C8-C10 triglyceride may be used in personal care products; mineral spirits, pine oil and d-limonene may be used in household and industrial cleaning products.

[0385] Table 41 shows emulsions formed with Examples 10-15 herein and oils and waxes that are important in personal care products, using PEG 400 dioleate, PEG 600 dioleate, sorbitan oleate + 5 ethylene oxide units, sorbitan oleate + 20 ethylene oxide units, castor oil + 25 ethylene oxide units, and castor oil + 40 ethylene oxide units as Comparative Examples. In some instances combinations of surfactants with differing HLBs may be more effective emulsifiers than individual surfactants used alone.

Table 40. Amount of surfactant that when mixed with 10% oil in water results in separation of emulsion after 24 hours

*Comparative Example

**Saybolt Universal Seconds

Table 41. Amount of surfactant that when mixed with 10% oil in water results in separation of emulsion after 24 hours

Comparative Examples

Solubility in electrolytes

[0386] The solubility of the surfactants in electrolytes was evaluated as an indicator of builder tolerance of the surfactants. Builders are typically used in household and industrial cleaners to provide alkalinity and soil dispersion. The solubility of surfactants in builders depends on builder concentration and is relatively insensitive to surfactant concentration above the critical micelle concentration.

[0387] To measure solubility of surfactants in electrolytes, mixtures of 10% salts and 5% surfactants were prepared, and water was added until the mixtures were clear at temperatures up to 50°C. The salts used as representative of builders were potassium tripolyphosphate (TKPP), sodium metasilicate, and potassium hydroxide. Table 42 shows results for surfactants of Examples 12-15 and Comparative Examples. Examples 10 and 11 were not sufficiently soluble in water to be included in this evaluation. The values in Table 42 represent the maximum concentration of the builder salt at which the surfactant was soluble. Table 12 also provides the calculated HLB for each of Examples 12-15 and Comparative Examples (NP-9 and NP-12, nonylphenol ethoxylate with an average of 12 ethoxylate units). Examples 13-15 (each with two ethoxylate chains) were highly soluble in the builder solutions, exhibiting greater solubility in electrolytes than NP-9 or NP-12. Example 12 (having a single ethoxylate chain and having a calculated HLB similar to that of NP-12) demonstrated similar solubility in electrolytes to NP- 12.

Table 42. Builder Tolerance

* Comparative Example Hard surface cleaning

[0388] Hard surface cleaning was evaluated according to ASTM D4488 A5 "Standard

Guide for Testing Cleaning Performance of Products Intended for Use on Resilient Flooring and Washable Walls" (now withdrawn by ASTM), which is incorporated herein by reference in its entirety. ASTM D4488 A5 involves soiling white vinyl floor tile with a mixture of oily and particulate soils, and cleaning with detergent-saturated sponges in a Gardner Scrubbability Apparatus. Formulations were prepared using 10% TKPP and 5% surfactant. Cleaning was evaluated at dilutions of 1/64 (2 fluid oz./gal.) and 1/128 (1 fluid oz./gal). Cleaning efficiency is determined by measuring reflectance at 45 degrees on a black-white scale of virgin tiles, soiled tiles and cleaned tiles. Table 43 shows results for Examples 11-15 and Comparative Example (NP-9). The percentage values in Table 43 indicate % soil removed from the tiles as measured by the reflectance (higher numbers indicate more soil has been removed). The least significant difference at 90% confidence for the measurements was 4.8%.

Table 43. Hard Surface Detergency measured according to ASTM D4488 A5.

* Comparative Example

Laundry Detergency

[0389] Laundry detergency was evaluated by formulating detergents at 10% surfactant and 2% soda ash to provide alkaline buffering. The detergent formulations were used at 1 gram/liter in a 100°F wash in tap water (about 60ppm hardness) in a Terg-O-Tometer. The swatches used were dust-sebum soiled fabrics (cotton and durable press fabric) from Scientific

Services S/D, Inc., Sparrow Bush, NY. For each wash, triplicate swatches were used. The results are reported as change in reflectance of the swatches before and after washing and are shown in Table 44 for Examples 11-15 and NP-9 as a Comparative Example. Larger numbers indicate more soil removed. The results show that Examples 12 and 13 were highly effective detergents under these conditions. Example 12 included a single ethoxylate chain with an average of 15 repeat units, and Example 13 included two ethoxylate chains each with an average of 5 ethoxylate units. Relative to Examples 12 and 13, detergency effectiveness decreased for

Example 11 (single chain ethoxylate with 10 ethoxylate units) and Example 15 (two ethoxylate chains each with 15 ethoxylate repeat units). Example 10 was not evaluated due to limited solubility. The experiment was repeated for Examples 12 and 13 with a different lot of soiled cloths from Scientific Services. The results of the additional laundry detergency tests are shown in Table 45. Also shown in Table 45 are measurements from additional nonyl phenol ethoxylates as Comparative Examples (NEODOL™ 25-7, 25-9, 45-13, 91-6, 91-8 surfactants, available from Shell Chemicals). In the second test, gel formation was not observed when the surfactants of Examples 12 and 13 were added to water.

Table 44. Laundry Detergency

* Comparative Example

Table 45. Laundry Deterg

* Comparative Examples

Examples 16-17: Preparation of alkyl-Capped Ethoxylate Surfactants

[0390] Two examples of ethyl-capped ethoxylated Diels-Alder adducts that may have utility as surfactants were made.

[0391] For Example 16, first a mixture of (E)-2-(2-(2-Ethoxyethoxy)ethoxy)ethyl 3-(4,8- dimethylnona-3,7-dien-l -yl)cyclohex-3-enecarboxylate and (E)-2-(2-(2- ethoxyethoxy)ethoxy)ethyl 4-(4,8-dimethylnona-3,7-dien-l-yl)cyclohex-3-enecarboxylate (compound 41-1 below) was prepared according to the following procedure.

41-1

Mixture of 1,3- and 1,4- isomers [0392] β-Farnesene (12.3 g, 60.1 mmol), 2-(2-(2-ethoxyethoxy)ethoxy)ethyl acrylate

(14.1 g, 60.1 mmol) and toluene (20 mL) were combined in a 250 mL round-bottomed flask equipped with a heating mantle, magnetic stirrer and reflux condenser. The mixture was stirred and heated to refluxing. After 30 hours the mixture was allowed to cool and the toluene removed under reduced pressure. The residual oil was subjected to kugelrohr distillation to provide 16.4 g (64.0 %) of the isomeric products as a pale yellow oil; bp 235 °C @ 0.08 torr.

[0393] A mixture of 2-(2-(2-Ethoxyethoxy)ethoxy)ethyl 3 -(4,8- dimethylnonyl)cyclohexanecarboxylate and 2-(2-(2-ethoxyethoxy)ethoxy)ethyl 4-(4,8- dimethylnonyl)cyclohexane-carboxylate (compound 41-2 below) was prepared according to the following procedure.

41-2

Mixture of 1,3- and 1,4-isomers

[0394] Compound 41-1 was placed in a 100 mL autoclave with 0.28 g of 5% Pd/C and

20 mL of ethyl acetate. After three evacuate/N₂ flush cycles the reactor was charged with hydrogen 400 psig) and the mixture stirred and heated to 75 °C. As the reaction proceeded the hydrogen pressure was periodically adjusted back to 400 psig. When hydrogen uptake had ceased the reactor was allowed to cool, the mixture filtered through Celite and the solvent removed under reduced pressure to afford 19.6 g (97.1%) of isomeric products as a colorless oil. ¹HNMR; (CDC1₃) δ 4.22 (m, 2H), 3.71-3.50 (m, 10H), 3.58 (t, J = 7.2 Hz, 2H), 2.54 (m, 0.3H), 2.25 (m, 0.7H), 1.96 (m, 2H), 1.80 (m, 1.4H), 1.58-1.00 (m, 16.6H), 1.21 (t, J = 7.2 Hz, 3H), 0.86 (d, J = 6.8 Hz, 6H), 0.84 (d, J = 6.8 Hz, 3H). ¹³CNMR; δ 196.2, 176.2, 70.7, 70.638, 70.609, 69.8, 69.3, 69.2, 66.6, 63.3, 63.2, 43.5, 43.4, 39.4, 37.5, 37.3, 37.033, 36.966, 32.8, 32.4, 32.3, 29.5, 29.4, 29.099, 29.042, 28.0, 26.1, 24.8, 24.5, 24.2, 22.7, 22.6, 19.7, 15.2.

[0395] For Example 17, first (E)-2-(2-Ethoxyethoxy)ethyl 3-(4,8-dimethylnona-3,7- dien-l-yl)cyclohex-3-enecarboxylate and (E)-2-(2-ethoxyethoxy)ethyl 3-(4,8-dimethylnona-3,7- dien-l-yl)cyclohex-3-enecarboxylate (compound 43-3 below) was prepared according to the following procedure.

43-3

Mixture of 1,3- and 1,4-isomers

[0396] Using the procedure for Example 16, excluding the toluene solvent that was used for making compound 41-1, 105 g (0.513 mol) of β-farnesene and 100 g (0.489 mol) of 2-(2- ethoxyethoxy)ethyl acrylate were combined in a 500 mL round-bottomed flask, stirred and heated to 110 °C for 40 hours. The reaction mixture was allowed to cool and the excess β- farnesene removed by kugelrohr distillation to provide 190 g (99%) of 43-3 as a colorless oil. ¹HNMR; (CDCls) δ 5.4 (s, br, 1H), 5.10 (s, br, 2H), 4.24 (m, 2H), 3.71, (m, 2H), 3.64 (m, 2H), 3.58, (m, 2H), 3.52 (t, J = 6.8 Hz, 2H), 2.57 (m, 1H), 2.34-1.84 (m, 14H), 1.67 (s, 3H), 1.60 (s, 6H), 1.21 (t, J = 6.8 Hz). ¹³CNMR; δ 175.9, 175.8, 137.3, 136.0, 135.0, 131.1, 124.4, 124.1, 120.3, 119.0, 70.7, 70.5, 69.9, 69.2, 69.2, 66.7, 63.4, 39.8, 39.7, 39.4, 37.7, 37.5, 30.6, 27.7, 26.8, 26.3, 25.7, 25.6, 25.2, 24.6, 17.7, 16.0, 15.2.

[0397] A mixture of 2-(2-Ethoxyethoxy)ethyl 3-(4,8- dimethylnonyl)cyclohexanecarboxylate and 2-(2-ethoxyethoxy)ethyl 4-(4,8- dimethylnonyl)cyclohexanecarboxylate (compound 43-4 below) was made according to the following procedure.

43-4

Mixture of 1,3- and 1,4-isomers

[0398] Using the procedure for compound 41-2 above 30.0 g of 43-3, 0.35 g of 5% Pd/C and 20 mL of hexane were combined in a 100 mL autoclave and heated to 90 °C under 800 psig of hydrogen for 18 hours to afford 24.6 g of 43-4 as a colorless oil. ¹HNMR; (CDCI3) δ 4.24 (m,

2H), 3.70 (m, 2H), 3.65 (m, 2H), 3.59 (m, 2H), 3.53 (2H, J = 6.8 Hz, 2H), 2.65-2.51 (m, 0.5H),

2.35-2.22 (m, 0.5H), 1.98 (m, 2H), 1.83-1.68 (m, 1H), 1.52 (m, 2H), 1.45-1.00 (m, 18H), 1.21 (t,

J = 6.8Hz, 3H), 0.87 (t, J = 6.8 Hz, 3H), 0.84 (t, J = 6.4 Hz, 3H). ¹³CNMR; δ 176.2, 176.1,

175.7, 175.5, 70.6, 69.9, 69.284, 69.254, 66.7, 63.246, 63.166, 43.5, 43.4, 40.6, 39.4, 37.7, 37.5,

37.3, 37.031, 36.961, 35.6, 35.5, 35.462, 32.8, 32.6, 32.5, 32.4, 32.3, 29.5, 29.4, 29.1, 29.0, 28.0,

26.2, 25.5, 24.8, 24.5, 24.247, 24.163, 22.7, 22.6, 19.7, 15.2.

Example 18: Epoxidation of n-butyl 4,8-dimethyl-nona-3,7-dienyl cyclohexene

carboxylates (mixture of 1,3 and 1,4 disubstituted isomers)

[0399] 4-(4,8-dimethylnona-3,7-dienyl)cyclohex-3-enecarboxylic acid n-butyl ester and

5-(4,8-dimethylnona-3,7-dienyl)cyclohex-4-enecarboxylic acid n-butyl ester (19a, 19b) is prepared according to any suitable method. For example, the procedure for Example 1 may be followed, except substituting n-butyl acrylate for methyl acrylate. A solution of the esters (19a,19b) (5.3 g, 16.0 mmol), in 150 mL ethyl acetate is cooled in an ice water bath and solid MCPBA (17.62 g, 77% max., 78.6 mmol theoretical) is added in 4 portions over 60 minutes. After the addition, the mixture is stirred at ice bath temperature for 1 hour and then at room temperature for 4 hours. The crude reaction mixture is washed twice with 100 ml 5% sodium bicarbonate solution and dried over solid potassium carbonate. The solution is filtered and concentrated to give about 4.8 g light yellow oil as a mixture of isomers, with a yield of about 76%. In some variations, each epoxy group can be hydro lyzed to result in hydro xyl groups on each of the carbon atoms forming the epoxy group using known techniques.

[0400] Partially epoxidized dicarboxylic acid esters derived from β-farnesene may be obtained in a similar manner using a higher ratio of starting ester to oxidant, e.g., so that the ratio of starting ester to oxidant is greater than about 1 :5, such as about 1 :4, 1 :3, 1 :2, 1 : 1 or 0.5:1.

Example 19: Preparation of Isosorbide diesters

47-3 [0401] Acrylic Acid/Farnesene Adduct Reaction with Isosorbide: Carboxylic acid

47-1 is prepared using any suitable technique. For example, a mixture of Compounds (la) and (lb) may be prepared according to the method of Example 1, and hydro lyzed with

KOH/Methanol using standard conditions. Carboxylic acid 47-1 (49.2 g, 0.178 mol) (mixture of 1,3- and 1,4- isomers), isosorbide (47-2, 12.4 g, 0.850 mol), /^-toluene sulfonic acid (100 mg) and 150 mL of toluene were placed in a 500 mL round-bottomed flask equipped with a magnetic stirrer, heating mantle and dean stark trap carrying a reflux condenser. The mixture was stirred and heated to refluxing. After three days the theoretical amount of water had collected in the trap and the mixture was allowed to cool to ambient temperature. The toluene was removed under reduced pressure and the residual oil chromatographed on a 24 cm X 6.5 cm column of silica gel with 20% ethyl acetate/hexane to remove a small amount of unreacted starting materials and monoester. Removal of the solvent afforded 32.8 g (58.6%>) of 47-3 (mixture of 1,3- and 1,4- isomers) as colorless oil.

[0402] Hydrogenation of Diester 47-3: Isosorbide diester 47-3 (32.8 g, 49.5 mmol),

10% Pd/C (Alfa Aesar, 0.25 g) and 20 mL of 1 : 1 ethyl acetate/hexane were combined in an autoclave. After three evacuate N₂ flush cycles the reactor was charged with 800 psig of hydrogen, stirred at 400 rpm and the mixture heated to 90 °C. As the reaction progressed the pressure was periodically brought back to 800 psig until hydrogen uptake ceased. The catalyst was removed by filtration and the solvents under reduced pressure to afford 32.5 g (97.3%>) of product 47-4 (mixture of 1,3- and 1,4- isomers) as thick colorless oil. The product was characterized by ¹HNMR.

Example 20: Preparation of Diels- Alder adduct between β-farnesene and 1,4- benzoquinone

MW=20₄.36 MW=108.10 MW=516.81

MF=C«H_M MF=C_RH,0,

Scheme 48

[0002] Procedure: In each of 3 separate pressure vessels, 1,4-benzoquinone (10.46 g,

96.8 mmol) was suspended in β-farnesene (39.5 g, 193 mmol). A magnetic stirring bar was place in each of the vessels and the three vessels were placed in a sandbath which was heated to

73 °C (thermocouple monitored near the vessels). Due to the nature of the setup, it is unlikely that the magnetic stir bar was sufficiently coupled with the magnetic stirrer to insure efficient stirring throughout the time of the reaction. The reaction mixture was heated in this manner for two days. On the third day, two of the three reaction mixtures were pulled from the sand bath.

One of the mixtures was dark brown and heterogeneous with dark solids in the bottom of the vessel. The other mixture was dark brown and homogeneous. The third mixture was also dark brown and homogeneous. Since there was a difference noted, a small amount from each of the two differing mixture was taken and combined for GC/MS analysis of the crude reaction mixture. GC/MS showed good conversion to the desired product (retention time -24 min; m/z =

516). Later that third day, on standing, the homogeneous reaction mixture which had been removed from the sand bath for sampling became rather thick with solids. The parallel reaction mixture which was heterogeneous on removing from the sand bath showed no noticeable change. 10 g of the "homogeneous" reaction mixture was placed on 300 mL of silica gel. The material was eluted using 1200 mL of petroleum ether wherein the top spot by TLC eluted

(likely unreacted farnesene). Eluting was continued with 2% ethyl acetate in petroleum ether

(500 mL), 4% ethyl acetate in petroleum ether (500 mL), and 6% ethyl acetate in petroleum ether (1000 mL) until the second fastest spot on TLC eluted completely. After evaporation of the volatiles from this second eluting compound, 5.34 g of product was obtained as a slightly yellow waxy solid. (A yellow band elutes at the leading edge of the product which may be a colored impurity). The remainder of this "third" of the reaction mixture was purified on 500 mL of silica gel by eluting first with petroleum ether (2L) followed by 6% Ethyl acetate to elute the product. Each of the remaining parallel reactions was also purified using this procedure. In total, 67.86 g (45% of theoretical) of product was obtained as a slightly yellow low melting waxy semi-solid after evaporation of the eluent.

Claims

CLAIMS What is claimed is:

1. A surfactant comprising or derived from a Diels-Alder adduct formed between a hydrocarbon terpene comprising a conjugated diene and a dienophile.

2. The surfactant of claim 1, wherein the dienophile is selected from maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, dialkyl maleates, dialkyl fumarates, dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates, (dialkylamino)alkyl acrylates, dialkyl acetylene dicarboxylates, vinyl ketones, maleimide and substituted maleimides, dialkyl azidocarboxylates, acetylene dicarboxylic acid, dialkyl acetylene dicarboxylates, vinyl sulfonates, vinyl sulfmates, vinyl sulfoxides, and combinations thereof.

3. The surfactant of claim 1, wherein the hydrocarbon terpene is β-farnesene.

4. The surfactant of claim 2, wherein the dienophile is selected from the group consisting of maleic anhydride, acrolein, a dialkyl maleate, a dialkyl fumarate, and an acrylic acid ester.

5. The surfactant of claim 1, wherein the hydrocarbon terpene is derived from a sugar using a genetically modified organism.

6. The surfactant of claim 1, adapted for use as a nonionic surfactant.

7. The surfactant of claim 6, wherein a hydrophilic portion of the Diels-Alder adduct comprises at least one alcohol group.

8. The surfactant of claim 7, having formula (J-7-IA), (J-7-IB) or a mixture thereof:

9. The surfactant of claim 7, having formula (J-7-IX):

10. The surfactant of claim 7, comprising one or more ethoxylated group having the formula

n represents an average number of ethoxylate units and is in a range from about 1 to about 200.

11. The surfactant of claim 10, wherein n is in a range from about 8 to about 20.

12. The surfactant of claim 10, comprising two ethoxylated groups having the

The surfactant of claim 10, having formula (J-7-IIA), (J-7-IIB), or a mixture

14. The surfactant of claim 10 having formula (J-7-X):

15. The surfactant of claim 6, comprising at least one glucose group.

16. The surfactant of claim 6, comprising at least one amine group.

17. The surfactant of claim 6, comprising at least one alkanolamide group.

18. The surfactant of claim 1 , adapted for use as an anionic surfactant.

19. The surfactant of claim 18, comprising a sulfate ion.

20. The surfactant of claim 18, comprising a sulfonate ion.

21. The surfactant of claim 1, adapted for use as a cationic surfactant.

22. The surfactant of claim 21, comprising a quaternary ammonium ion.

23. The surfactant of claim 1, adapted for use as a zwitterionic surfactant.

24. The surfactant of claim 23, comprising an amine-oxide group.

25. The surfactant of claim 1, adapted for use in a detergent, emulsifier, or personal care product.

26. The surfactant of claim 1, having a surface tension at 0.01% of about 20 mN/m or less.

27. A surfactant comprising a cyclohexyl ring, at least one hydrophobic tail attached to the cyclohexyl ring, and one or more hydrophilic heads attached to the cyclohexane ring, wherein the at least one hydrophobic tail originates from a hydrocarbon terpene comprising a conjugated diene.

28. The surfactant of claim 27, comprising one hydrophobic tail and one hydrophilic head attached to the cyclohexyl ring.

29. The surfactant of claim 27, comprising one hydrophobic tail and two hydrophilic heads attached to the cyclohexyl ring.

30. The surfactant of claim 27, comprising two hydrophobic tails and one hydrophilic head attached to the cyclohexyl ring.

31.The surfactant of claim 27, comprising two hydrophobic tails and two hydrophilic heads attached to the cyclohexyl ring.

32. The surfactant of claim 27, wherein the hydrocarbon terpene is β-farnesene.

33. The surfactant of claim 32, wherein the β-farnesene is derived from a sugar using genetically modified organisms.

34. The surfactant of claim 32, comprising at least 30% carbon atoms derived from modern carbon sources.

35. The surfactant of claim 27, adapted for use as a nonionic surfactant.

36. The surfactant of claim 27, adapted for use as an anionic surfactant.

37. The surfactant of claim 27, adapted for use as a cationic surfactant.

38. The surfactant of claim 27, adapted for use as a zwitterionic surfactant.

39. The surfactant of claim 27, adapted for use as an emulsifier, laundry detergent, or personal care product.

40. A method of making a surfactant, comprising reacting a hydrocarbon terpene comprising a conjugated diene with a dienophile to form a Diels-Alder adduct that is capable of acting as a surfactant, wherein the hydrocarbon terpene is selected to impart a desired degree of hydrophobicity to the adduct and the dienophile is selected to impart a desired degree of hydrophilicity to the adduct.

41. The method of claim 40, wherein the hydrocarbon terpene is β-farnesene.

42. The method of claim 40, comprising obtaining the hydrocarbon terpene from a genetically modified organism.

43.A method of making a surfactant, comprising reacting a hydrocarbon terpene comprising a conjugated diene with a dienophile to form a Diels-Alder adduct, and chemically modifying a residue of the dienophile in the adduct to form a surfactant comprising a desired degree of hydrophilicity, wherein a residue in the adduct from the hydrocarbon terpene imparts a desired degree of hydrophobicity to the surfactant.

44. The method of claim 43, wherein the hydrocarbon terpene is β-farnesene.

45. The method of claim 43, comprising obtaining the hydrocarbon terpene from a genetically modified organism.

46. A personal care formulation comprising the surfactant of any one of claims 1-26.

47. A personal care formulation comprising the surfactant of any one of claims 27-39.

48. A laundry detergent formulation comprising the surfactant of any one of claims 1-26.

49. A laundry detergent formulation comprising the surfactant of any one of claims 27-

39.

50. A hard surface cleaner formulation comprising the surfactant of any one of claims 1-

26.

51.A hard surface cleaner formulation comprising the surfactant of any one of claims 27-

39.

52. An emulsifier comprising the surfactant of any one of claims 1-26.

53. An emulsifier comprising the surfactant of any one of claims 27-39.