**Abstract**

Unlike other crops, the jojoba shrub contains around 50% by weight of an almost odorless, colorless oil made mostly of monoesters of the straight-chain alcohols and acids, C20 and C22, with one double bond on either side. The shrub is distinct from other species. In order to create modified jojoba derivatives, scientists can modify both the olefinic group and the ester group of jojoba oil, which is detailed in this book chapter. Jojoba oil has been modified in studies for various uses. These alterations include isomerization, bromination, sulfur-chlorination, sulfurization, hydrogenation, epoxidation, hydroxymethylation, phosphonation, ethoxylation, Diels-Alder adduction, pinacol rearrangement, bonding with polyethylene, and boning with polystyrene matrix. The next paragraphs will cover all of the applications for these modified jojoba oil derivatives, including medicine, emulsifiers, detergents, surfactants, lubricating oil, lubricating oil additives, leather tanning, texture, and corrosion inhibitors.

**Keywords:** jojoba oil, spectrophotometric elucidation of jojoba oil, ester group reactions, C=C group reactions, applications of jojoba oil

## **1. Introduction**

Jojoba shrub is a drought-resistance shrub from Arizona, California, and Mexico indigenous [1–3]. Simmondsia chinensis is the evergreen and drought resistance. It can grow between 0.6 and 5 m in height and its roots can grow to 10 m in length. Jojoba's shrub, which means either male or female (poisonous), produces flowers. Jojoba shrub is dioecious. The flowers will be pollinated by the wind at the end of March and by August, when the flowers will mature complete by October [4, 5].

#### **1.1 General characteristics of jojoba oil**

Jojoba is a vegetable oil obtained from desert shrub seeds native to Arizona, California, the North-West of Mexico, and Baja California (*China simmondsia*). The jojoba oil obtained differs from most other vegetable and animal oils because it is not a fat but a fluid wax [6]. Jojoba oil is unique in vegetable oils, since sperm oil is unique in animal oils. Never before has such a vegetable oil been accessible in commercially accessible amounts to sector. It has a liquid ester combination of 97%. It is a nondrying oil with elevated oxidation resistance, which can be stored without being rancid for years; its lubricity; its unsaturation (double bonds). The following are valued for the jojoba oil. It has its natural purity and molecular simplicity and stabilization [1, 2].

### **1.2 Extraction of jojoba oil**

The extraction of jojoba oil from seeds has several techniques [6–9]. Spadro et al. [9] used filtration—extraction process for extraction of jojoba oil. This method consists mainly of: 1) cooking oil seeds are flaked at reduced temperatures and greater humidity than usual in hydraulic and screw-pressure cooking; 2) crushing the baked material by evaporative cooling; 3) slurry of the material with a filter, and 4) filtration of the slurry and a counter that is being washed by a rotary vacuum filter. The pressing and leaching of jojoba oil were researched by Abu Arabi et al. [7]. Mechano-pressing of the plants with or without application of heat in a method called expeller-pressing is the most direct extraction method of jojoba oil [7]. Cold-pressing and second-pressing are purely mechanical techniques used for extracting jojoba oil. The jojoba oil is usually filtered and screened after mechanical removal. Jojoba oil is subsequently pasteurized for safety and quality assurance.

### **1.3 Jojoba oil physical characteristics**

Raw jojoba oil is a light gold fluid, has little impurity, and needs little or no refining for most reasons. There are no resins, tars, and alkaloids and there are only traces of wax, steroids, tocopherols, and hydrocarbons. It is generally unnecessary to neutralize oil because the fatty acids are generally small. While bleaching is generally also unnecessary, easy business methods can be applied to remove and generate yellow pigments. Oil is frequently pasteurized to kill microorganisms for cosmetic and pharmaceutical purposes. Working with jojoba oil is simple. It is nontoxic and organically degradable. It is easily solved with benzene, petroleum ether, chloroform, carbon tetrachloride, and carbohydrate disulfide, but it does not contain methanol or acetone [10]. The oil has promising physical properties for numerous industry demands; high viscosity index, high flash and fire points, high dielectric consistency, and high stability. The composition of its low volatility is little influenced by repeated heating up to extremely elevated temperatures. Kuss et al. [11] have produced comprehensive density, compression, and viscosity measures in jojoba oil. Jojoba oil has conductivity values in the range of 34–140o C comparable to oleic acid.

### **1.4 Chemical properties of jojoba oil**

The raw natural extract contains 97% linear wax esters (the rest consists of free fatty alcohols and acids and tocopherols) because of their molecular homogeneity. The oil contains two C=C and one ester group, which enable the oil to make all alkenes reactions and all esters reactions. It also has incredible acid/alcohol combinations with C20 or C22 carbon atoms chain lengths. Common vegetable oils have, by comparison, fatty acids, mostly 16- and 18-carbon long chain. The esters are almost completely comprised of straight and alcohol chain acids [6, 8, 10, 11]. Iodine value, peroxide value, saponification value, unsaponifiable matter, and acid value are the most significant chemical features in jojoba oil (**Table 1**).

*The Vital Uses of Jojoba Oil and Its Derivatives in Daily Life and the Petroleum Industry DOI: http://dx.doi.org/10.5772/intechopen.108200*


*Oil from expeller-pressed jojoba seeds start to freeze at 10.6°C (51°F). It solidifies into a thick paste at 7o C. Frozen oil, allowed to warmup, melts at 7°C (45°F).*

*Smoke and flash points are determined according to the official method, Cc 9a-48, of the American Oil Chemists***'** *Society.*

*Saybolt Universal seconds.*

*SOURCE: T. K. Miwa [12].*

#### **Table 1.**

*Physical and chemical properties of jojoba oil.*

#### **1.5 Structure of jojoba oil**

The structure of jojoba oil was elucidated, the double bond positions were almost exclusively ω-9, i.e., the ethylenic bond was between the 9th and 10th carbon atoms when counting from the methyl or terminal end of the backbone carbon chain. A small amount of the hexadec-9-enoic (0.1%) and octadec-11-enoic (1%) acids of ω-7 homologs have been found. All ethylenic bonds were cis in geometric configuration. Jojoba wax ester molecules are generally 98% cis- monounsaturated at the ω-9 position at both ends of the molecules. **Figure 1** shows the molecular structure of the jojoba wax esters. Where (n) is 5, 7, and 9 and (m) is 10, 12, and 14, based on the environment in which the plant has grown [13, 14].

#### *1.5.1 Elucidation of chemical structure of jojoba oil*

#### *1.5.1.1 Using gas chromatographic analysis*

In 1971, Miwa elucidated the structure of different types of jojoba oil [15]. In 1984, Miwa investigated the structure of jojoba oil. The sections are supplied as a single molecular species within a particular chain length [16]. Cis 13-docpsenyl Cis-11 eicosenoate or trivial name is a primary component (37%) followed by jojobenyl

**Figure 1.** *Structure of jojoba wax.*

jojobenoate (24%) and jojobenyl erucate (10%). Cis-11-eicoseneic (jojobene) is the primary acid (71%), followed by erucic (14%), and oleic (10%). Erucyl (45%) is the primary alcohol, and alcohol (jojobenyl) closely follows. The primary component in the lowest median molecular weight was jojobenyl (46%) instead of erucyl (42%).

#### *1.5.1.2 Using GC/MS*

Gayland et al. [17] determined the double bond positions in the fatty acids by GC/MS of their methoxy derivatives. Jojoba oil wax esters were assumed to be ω9-unsaturated. Until a report indicated that several isomeric fatty alcohols were present. After a sample of the Apache oil had been saponified and the methyl esters, derived from the fatty acids, and alcohols separated, methoxy derivatives were formed and subjected to GC/MS. The derivatives of the methyl esters showed only small amounts of positional isomers other than ω9, and only in the 16:1 (0.1% ω7) and 18:1 (1.0% ω7).

#### *1.5.1.3 Using high-pressure liquid chromatography*

Gayland et al., 1977 used high-pressure liquid chromatography (HLPC) to separate components according to chain length. When they use high-pressure liquid chromatography on a new micro-particulated reverse phase, rapid separation of long-chain triglycerides and wax esters by chain length and degree of unsaturation. Since the acids and alcohols of jojoba oil are virtually all monoenes, each peak in the chromatogram of jojoba oil contained the combinations of ester and alcohol of one chain length [17].

#### *1.5.1.4 Using X-ray diffraction analysis*

Simpson and Miwa [18] studied the structure of hydrogenated jojoba wax using X-ray diffraction analysis. They found that the chain shape is extended completely with ortho-rhombic 0⊥ perpendicular to packaging. In addition to the ester connection, the jojoba conformation appears to be unlike polyethylene. The jojoba unit cell is fundamentally rectangular and approximates the cell of polyethylene, compared to its oblique mono-clinical unit cells of long-chain esters earlier studied. The wax ester research shows mild chain tilt in relation to the abdominal plane. It is similar to polyethylene and contrasts again with the earlier researched esters. They found, finally, that hydrogenated jojoba wax appears to be more prevalent in polyethylene than in its own chemical generation.

#### *1.5.1.5 Using differential scanning calorimetry*

In 1996, DSC thermographs of native jojoba liquid wax esters were studied by David et al. [19] and found that one endothermal occurrence with a peak intake of *The Vital Uses of Jojoba Oil and Its Derivatives in Daily Life and the Petroleum Industry DOI: http://dx.doi.org/10.5772/intechopen.108200*

**Figure 2.** *Transesterification of hydrogenated jojoba wax esters. Source: David et al. [19].*

4.358°C, a maximum peak of 11.818°C and a total of 123.564 J/g, had been given by the thermogram of DSC for the native Jojoba liquid wax esters, while thermograms with fully hydrogen jojoba-wax esters were at their peak beginning, at a maximum of 67,575°C, and at a top maximum, at oscillating 69,066°C and at oscillating ∆HC of 218,269 J/g (**Figure 2**). Native wax esters, mainly the unsaturated shape, gave the 13.5°C falling point beyond the maximum DSC observed. However, compared to the maximum 69.1°C DSC, the fully saturated wax esters have a drop point of 72.3°C, as the dripping points are close to the highest DSC, the "A" endothermic event is diunsaturated, and "C" is a fully saturated event, which is a maximum of 69.1°C.

The DSC thermograms for the trans-esterified wax esters indicated that transesterified wax ester mixtures with 5 and 10% saturation have produced the two endothermic events marked A for the event at around 5°C and B at around 20°C; the 3rd endotherm is first observed at 15% saturation at around 45°C and is increasing in saturation by 50% [19].

#### *1.5.1.6 By determination of oxidative stability*

The oxidative stability of wax esters was determined by a thermogravimetric analysis in 1979 by Hagemann and Rothfus [20]. The relative oxidative stability of sperm whale oil and 8 wax ester preparations is determined by comparing oxidization profiles that have been corrected for ester volatility. They found that, although more volatile, wax esters with unsaturation near the ester bond are as stable for oxidation as those with double bonding close to the center of each aliphatic chain. The oxidative stability of jojoba wax was determined by Arieh et al. [21]. The autoxidation of crude, bleaching, and striped jojoba wax was measured by speeds with accelerated oxidation (98°C), and the long induction of raw yellow wax (30 h) was observed by raw yellow oxidation compared with bleached wax (10–12 h) and striped waxes (2 h). A 0.02% hydroxytoluene or butylated hydroxy anisole was added to the wax and even improved its stability. Wax autoxidation was also considered at room temperature. In presence of light and air, the activity of the natural inhibitor was lost rapidly.

### **2. Modification of jojoba wax**

A change or modification is usually made to improve something. The presence of two double bonds at jojoba (one each in the alcohols and acids moieties) as well as the ester group provides lot of scope to modify the oil [22]. Chemical modification of jojoba oil varies according to the type of attack occurs into: (i) attack at the ester group, "trans-esterification, hydrolysis, saponification, hydrogenlysis, ammonolysis, quaternary ammonium salt," (ii) attack at the double bond including, "geometrical isomerization of double bond, hydrogenation, halogenation, sulfurization, halosulfurization, oxygenation, epoxidation, phosphonation, phosphosulphidation, alkylation, oxidation, episulphidation and polymerization". These reactions will be discussed in the following paragraphs.

#### **2.1 Isomerization of jojoba**

In 1982, Brown and Olenberg [23] found that acidic bentonite clays initiate the isomerization of the cis configurations over a certain temperature when contacting jojoba oil. The technique of preparing jojoba oil isomerates melting above 25°C was used, consisting of the measures of contact between jojoba oil and acidic bentonite type clay at temperatures in the area between 150 and 350°C for adequate moment in order to instill in an adequate amount an isomerate with a melting process from natural cis configuration to a trans configuration. In 1984, Galun and Shaubi [24] perfumed jojoba wax over a variety of temperatures in a thermal insulation. They are isomerized to a temperature between 250°C and 400°C in the vacuum-sealed ampoules. The specimens have been heated for 192hrs at 53.3% trans jojoba wax isomerized at 300°C to 37.6% partially decomposed. Heating up 65% brassy in vacuumsealed ampoules for 216 hrs at a rate of 300°C to 38%.

In 1984, Galun and Shaubi [24] were photosensitizing to investigate the cis-trans isomerization of jojoba wax. In the presence of sensitizers, wax solutions from jojoba have been radiated at room temperature over 366 nm at wavelengths. Only sensitizers with triple energy greater than 68kcal/mol have been isomerized by cis-trans. Quantum yields were low and the photostationary state achieved the conversion of up to 25% of the trans isomers. The general mechanism of the photosensitized process was originally proposed by Hammond et al. [25] and has been broadly applied.

#### **2.2 Diels-Alder adducts of jojoba**

The reaction of Diels-Alder is an organic chemical reaction [4 + 2] that forms a cyclohexene substituted system, between the conjugate diene and an alkene substituted, usually called the dienophile. In 1928, Otto Paul Hermann Diels and Kurt Alder described it for the first time and in 1950 they were awarded the Nobel Prize for chemical medicine. In 1982, Shani [26] introduced new jojoba adducts based on Diels-Alder reaction of jojobatetraene with three typical dienophiles (maleic anhydride, N-methylmaleimide, and acrylonitrile). Shani [27] also reacted oxygen with a conjugated diene to form cyclic peroxide, which lead to the formation of a furan derivative.

#### **2.3 Oxidation of jojoba oil**

In 1984, Galun et al. [28] examined the use of potassium permanganate and hydrogen peroxide for the oxidation of jojoba wax. Using the appropriate stage catalyst transfer, permanganate in aqueous structures oxidized the double bonds to carboxylates. Wax reaction in the acid formats, which was then hydrolyzed into nearby glycols, was caused by hydrogen peroxide. The hydrogen peroxide oxidation of these di-glycols was benzoylated.

#### **2.4 Halogenation of jojoba wax**

#### *2.4.1 Chlorination of jojoba wax*

In 1984, Gulan et al. investigated the halogenation of jojoba wax [28], including allylic chlorination with jojoba wax in organic solvents with t-butyl hypochlorite. They noted that when jojoba wax was reacted in presence of benzoyl peroxide with two equivalents of t-butyl hypochlorite, the di-chloro derivative was given. Chlorine

#### *The Vital Uses of Jojoba Oil and Its Derivatives in Daily Life and the Petroleum Industry DOI: http://dx.doi.org/10.5772/intechopen.108200*

atoms seemingly have a double bond on both sides. Chlorination of two equivalents of t-butyl hypochlorite without benzoyl peroxides as a catalyst also applies to the product of allylic, but there was also some addition to the double bond. In the presence of benzoyl peroxide as a catalyst, jojoba wax with four equivalents of t-butyl hypochlorite was combined with a compound of allylic chlorination and double bonding as well. Jojoba wax responded to the addition compound (VIII) by combining t-butyl hypochlorite and 6-chlorohexanol in benzene.

### *2.4.2 Bromination of jojoba*

Shani added bromine to jojoba oil and trans-isomer [29], which, with the removal, provided the acetylene and allene components, respectively, if the base is excessively reacted. When limited base volumes were used, allylic bromine of liquid wax and transisomer and later HBr removal, the bromoolefinic products resulted in the two conjugated diene systems in either side of the ester (jojoba tetraene). Jojoba oil and trans-jojoba oil were also brominated using N-bromo succinamide (NBS). Two hexabromo-jojoba isomers were produced by Shani [30] in 1988 with bromine added to the bromoolefinic and bromolylic derivatives and one by jojobatetraine. Bis-Jojoba wax allylic or jojobatetraen monolylic bromination and HBr removal produced jojobahexaene which has two conjugated triene units on both components of the ester. In 2017, Rabab [12] prepared tertrabromojojoba via direct bromination of jojoba oil in an ice bath.
