ullmann's encyclopedia of industrial chemistry || dicarboxylic acids, aliphatic

Dicarboxylic Acids, Aliphatic

BOY CORNILS, Hoechst AG, Frankfurt, Germany

PETER LAPPE, Ruhrchemie AG, Oberhausen, Germany

UPDATED BY STAFF

1. Introduction . . . . . . . . . . . . . . . . 1

2. Saturated Dicarboxylic Acids . . . . 2

2.1. Physical Properties . . . . . . . . . . . 2

2.2. Chemical Properties . . . . . . . . . . 2

2.3. Production . . . . . . . . . . . . . . . . . 4

2.3.1. Degradative Methods . . . . . . . . . 4

2.3.2. Processes Maintaining the CarbonStructure . . . . . . . . . . . . . . . . . . 5

2.3.3. Syntheses from Smaller Units . . . 7

2.4. Individual Saturated Dicarboxylic

Acids . . . . . . . . . . . . . . . . . . . . . 8

2.4.1. Succinic Acid . . . . . . . . . . . . . . . 82.4.2. Glutaric Acid. . . . . . . . . . . . . . . 9

2.4.3. Dimethylglutaric Acids . . . . . . . . 92.4.4. Trimethyladipic Acid . . . . . . . . . 92.4.5. Pimelic Acid . . . . . . . . . . . . . . . 9

2.4.6. Suberic Acid . . . . . . . . . . . . . . . 102.4.7. Azelaic Acid . . . . . . . . . . . . . . . 102.4.8. Sebacic Acid . . . . . . . . . . . . . . . 10

2.4.9. 1,12-Dodecanedioic Acid. . . . . . . 112.4.10. 1,13-Tridecanedioic Acid (Brassylic

Acid). . . . . . . . . . . . . . . . . . . . . 11

2.4.11. C19 Dicarboxylic Acids . . . . . . . . 113. Unsaturated Dicarboxylic Acids . . 12

3.1. Physical Properties . . . . . . . . . . . 12

3.2. Chemical Properties . . . . . . . . . . 12

3.3. Production . . . . . . . . . . . . . . . . . 12

3.4. Individual Unsaturated Dicarboxylic

Acids . . . . . . . . . . . . . . . . . . . . . 14

3.4.1. Itaconic Acid . . . . . . . . . . . . . . . 143.4.2. Dimer Acids . . . . . . . . . . . . . . . 144. Quality Specifications and Analysis 15

5. Storage, Transportation, and

Handling . . . . . . . . . . . . . . . . . . 15

References . . . . . . . . . . . . . . . . . 15

1. Introduction

Aliphatic v,v0-dicarboxylic acids (or diacids)can be described by the following generalformula:

HOOC� CH2ð Þn � COOH

According to IUPAC nomenclature,dicarboxylic acids are named by adding thesuffix dioic acid to the name of the hydrocarbonwith the same number of carbon atoms, e.g.,nonanedioic acid for n ¼ 7. The older literatureoften uses another system based on the hydro-carbon for the (CH2)n carbon segment and thesuffix dicarboxylic acid, e.g., heptanedicarbox-ylic acid for n ¼ 7. However, trivial names arecommonly used for the saturated linear ali-phatic dicarboxylic acids from n ¼ 0 (oxalicacid) to n ¼ 8 (sebacic acid) and for the simple

unsaturated aliphatic dicarboxylic acids; thesenames are generally derived from the naturalsubstance in which the acid occurs or fromwhich it was first isolated.

Aliphatic dicarboxylic acids are found innature both as free acids and as salts. Forexample, malonic acid is present in smallamounts in sugar beet and in the green partsof the wheat plant; oxalic acid occurs in manyplants and in some minerals as the calcium salt.However, natural sources are no longer used torecover these acids.

The main industrial process employed formanufacturing dicarboxylic acids is the ring-opening oxidation of cyclic compounds.

Adipic acid is the most importantdicarboxylic acid. Oxalic, malonic, suberic,azelaic, sebacic, and 1,12-dodecanedioic acids,as well as maleic and fumaric acids, are alsomanufactured on an industrial scale.

# 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim10.1002/14356007.a08_523.pub3

Dicarboxylic acids are important feedstocksin the manufacture of polyamides or of di- andpolyesters. Esters produced by the reactionof dicarboxylic acids with monofunctionalalcohols serve as plasticizers or lubricants. Inaddition, dicarboxylic acids are used as inter-mediates in many organic syntheses.

2. Saturated Dicarboxylic Acids

The most important saturated aliphaticdicarboxylic acids are treated under separatekeywords (see ! Adipic Acid, ! MalonicAcid and Derivatives, ! Oxalic Acid).

2.1. Physical Properties

Dicarboxylic acids are colorless, odorless crys-talline substances at room temperature. Table 1lists the major physical properties of somesaturated aliphatic dicarboxylic acids.

Thelowerdicarboxylicacidsarestrongeracidsthan the corresponding monocarboxylic ones.The first dissociation constant is considerablygreater than the second. Density and dissociationconstants decrease steadily with increasing chainlength. By contrast, melting point and watersolubility alternate: Dicarboxylic acids with aneven number of carbon atoms have highermelting points than the next higher odd-numbereddicarboxylicacid. In then¼0–8range,dicarboxylicacidswithanevennumberofcarbonatoms are slightly soluble in water, while thenext higher homologues with an odd number ofcarbon atoms are more readily soluble. As chainlength increases, the influence of the hydrophiliccarboxyl groups diminishes; from n¼ 5 (pimelicacid) onward, solubility in water decreasesrapidly. The alternating solubility of dicarboxylicacids can be exploited to separate acid mixtures[1, 2]. Most dicarboxylic acids dissolve easily inlower alcohols; at room temperature, the lowerdicarboxylic acids are practically insoluble inbenzene and other aromatic solvents.

2.2. Chemical Properties

The chemical behavior of dicarboxylic acids isdetermined principally by the two carboxylgroups. The neighboring methylene groups

are activated generally to only a minor degree;malonic acid derivatives (esters and nitriles)are an exception (! Malonic Acid andDerivatives).

Thermal decomposition of dicarboxylicacids gives different products depending onthe chain length. Acids with an even numberof carbon atoms require higher decarboxylationtemperatures than the next higher odd-num-bered homologues; lower dicarboxylic acidsdecompose more easily than higher ones. Toavoid undesired decomposition reactions, ali-phatic dicarboxylic acids should only be dis-tilled in vacuum. When heated above 190 �C,oxalic acid decomposes to carbon monoxide,carbon dioxide, and water. Malonic acid isdecarboxylated to acetic acid at temperaturesabove 150 �C:

HOOC� CH2 � COOH ! CH3COOHþ CO2

When malonic acid is heated in the presenceof P2O5 at ca. 150

�C, small amounts of carbonsuboxide (C3O2) are also formed. Succinic andglutaric acids are converted into cyclic anhy-drides on heating:

When the ammonium salt of succinic acid isdistilled rapidly, succinimide is formed, withthe release of water and ammonia.

Higher dicarboxylic acids from n¼ 4 (adipicacid) to n ¼ 6 (suberic acid) split off carbondioxide and water to form cyclic ketones:

The decomposition of still higherdicarboxylic acids leads to complex mixtures.With the exception of oxalic acid, dicarboxylicacids are resistant to oxidation. Oxalic acid isused as a reducing agent for both commercialand analytical purposes. Dicarboxylic acidsreact with dialcohols to form polyesters and

2 Dicarboxylic Acids, Aliphatic

Tab

le1.

Physicalproperties

ofsaturateddicarboxylicacids

IUPA

Cname

Com

mon

name

CAS

registry

number

Formula

Mr

mp,

� Cbp

at13.3kP

a,� C

Rat

25� C

,g/cm

3Solubility

inH2O

at20

� C,

wt%

Decar-

boxylation

temperature,

� C

Ionization

constants

K1

K2

Ethanedioicacid

oxalicacid

[144-62-7]

HOOC–COOH

90.03

189.5

(sublimes)

1.653

8.0

166–180

5.36

�10�

25.42�1

0�5

Propanedioicacid

malonicacid

[141-82-2]

HOOC–CH2–COOH

104.06

135

1.619(16�C)

73.5

140–160

1.42

�10�

32.01�1

0�6

Butanedioicacid

succinicacid

[110-15-6]

HOOC–(CH2) 2–COOH

118.08

188

235a

1.572

5.8

290–310

6.21

�10�

52.31�1

0�6

Pentanedioicacid

glutaricacid

[110-94-1]


132.11

99200(2.7kP

a)1.424

63.9

b280–290

4.58

�10�

53.89�1

0�6

2,2-Dim

ethylpentanedioic

acid

2,2-dimethylglutaric

acid

[681-57-2]

1d160.17

855.25

�10�

53.8�

10�6

Hexanedioicacid

adipicacid

[124-04-9]


146.14

153

265

1.360

1.6

300–320

3.85

�10�

53.89�1

0�6

2,4,4-Trimethylhexanedioic

acid

2,4,4-trim

ethyladipic

acid

[3937-59-5]

2188.22

681.075c

Heptanedioicacid

pimelicacid

[111-16-0]


160.17

106

272

1.329(15�C)

5.0

290–310

3.19

�10�

53.74�1

0�6

Octanedioicacid

subericacid

[505-48-6]


174.19

144

279

1.266

0.16

340–360

3.05

�10�

53.85�1

0�6

Nonanedioicacid

azelaicacid

[123-99-9]


188.22

108

287

1.225

0.24

320–340

2.88

�10�

53.86�1

0�6

Decanedioicacid

sebacicacid

[111-20-6]


202.25

134.5

295

1.207

0.10

350–370

3.1�

10�5

3.6�

10�6

Undecanedioicacid

[1852-04-6]


216.27

110

0.014

Dodecanedioicacid

[693-23-2]


230.30

131

254(2.0kP

a)0.004

Tridecanedioicacid

brassylicacid

[505-52-2]


244.33

114

1.150(18�C)

0.00

25Tetradecanedioicacid

[821-38-5]


258.35

129

aFormstheanhydride(101.3

kPa).

bReadily

solublein

water.

cMixture

of40%

2,2,4-

and60%

2,4,4-trim

ethyladipicacid.

d1¼

HOOC–C(CH3) 2–(CH2) 2–COOH

2¼

HOOC–CH(CH3)–

CH2–C(CH3) 2–CH2–COOH

Dicarboxylic Acids, Aliphatic 3

with diamines to form polyamides. They alsoserve as starting materials for the production ofthe corresponding diamines. Reaction withmonoalcohols yields esters. All of thesereactions are commercially important. Severalreactions with malonic and glutaric acids are ofinterest in organic syntheses: the Knoevenagelcondensation, Michael addition, and malonicester synthesis (! Malonic Acid and Deriva-tives) [3, 4].

Succinic acid ester reacts with aldehydes orketones in the presence of sodium ethoxide orpotassium tert-butoxide to form alkylidene-succinic acid monoesters (Stobbe condensa-tion). These can subsequently be convertedinto monocarboxylic acids by hydrolysis,decarboxylation, and hydrogenation [5]:

Cyclic ketones are obtained from C6��C8

dicarboxylic acid esters and sodium methoxide(Dieckmann reaction) [6]. Esters of adipic,pimelic, and suberic acids can be convertedin good yields; esters of higher dicarboxylicacids cannot be cyclized by this method.

Acyloin condensation with metallic sodiumgives cyclic acyloins; this method is particu-larly suitable for synthesis of large rings [7]:

Detailed summaries of reactions withdicarboxylic acids can be found in [8].

2.3. Production

A number of straight-chain aliphaticdicarboxylic acids and their derivatives occurin nature. However, isolation from natural sub-stances has no commercial significance.Although many syntheses for the productionof aliphatic dicarboxylic acids are known, onlya few have found industrial application. This isdue partly to the shortage of raw materials.

The most important processes for the manu-facture of saturated aliphatic dicarboxylic acidsare the following:

1. Oxidative cleavage of cyclic compounds(e.g., adipic acid from cyclohexane,1,12-dodecanedioic acid from 1,5,9-cyclododecatriene)

2. Oxidative cleavage of unsaturated mono-carboxylic acids (e.g., azelaic acid fromoleic acid)

3. Alkaline cleavage of substituted mono-carboxylic acids (e.g., sebacic acid fromricinoleic acid)

4. Hydrogenation of unsaturated dicarboxylicacids (e.g., succinic acid from maleic acid)

5. Oxidation of v, v0-diols (e.g., pimelic acidfrom 1,7-heptanediol)

6. Carbonylation reactions (e.g., suberic acidfrom 1,6-hexanediol)

Some special syntheses are also of interest.The following sections treat the most importantmanufacturing processes, which can be subdi-vided into degradative methods, processes inwhich the carbon structure is maintained, andsynthetic methods starting from smaller units.

2.3.1. Degradative Methods

Ozonolysis of Oleic Acid. Ozonolysis of oleicacid [112-80-1] followed by oxidative cleavagegives pelargonic acid [112-05-0] and azelaicacid [9]:

Figure 1 shows a commercial process for theproduction of azelaic acid from oleic acid.


Oleic acid is cleaved by ozonolysis (O3 con-centration in the air: 1.0 vol %) at 20–40 �Cin pelargonic acid and water. The alkene resi-dence time is about 10 min. The ozonide is thencleaved with oxygen at 70–110 �C. Pelargonicand azelaic acids are separated from higherboiling compounds by subsequent distillation.Azelaic acid is subjected to extraction to removemonocarboxylic acids; distillation of the extrac-tant finally yields pure acid.

Cleavage of Ricinoleic Acid. Alkaline cleav-age of ricinoleic acid [141-22-0] (12-hydroxy-9-octadecenoic acid) under pressure and at hightemperature leads to the formation of sodiumsebacate and 2-octanol [10]:

In industry, castor oil [8001-79-4], whichcontains about 87 % ricinoleic acid, is normallyused instead of the pure acid.

Oxidation with N2O4. Oxidative degradationof monocarboxylic acids generally producesdicarboxylic acid mixtures; the compositionof the reaction products shifts toward the higherdicarboxylic acids as the chain length of the

monocarboxylic acids increases. Oxidation ofstearic acid [57-11-4] with N2O4 yields a mix-ture consisting mainly of sebacic and caprylic[124-07-2] acids. In the sameway, palmitic acid[57-10-3] can be oxidized with nitric acid–N2O4 to form suberic acid [11].

Commercial production of adipic acidfrom cyclohexanol–cyclohexanone yields twomajor byproducts, succinic and glutaric acids,which can be separated easily (! Adipic Acid,Chap. 4).

Oxidation of Hydrocarbons. Oxidative degra-dation of hydrocarbons is also a common man-ufacturing process. The best-known example isthe oxidation of benzene to maleic acid bymeans of vanadium pentoxide catalysts (!Maleic and Fumaric Acids).

2.3.2. Processes Maintaining the CarbonStructure

Cleavage of Cyclic Compounds. Many pro-cesses for the manufacture of dicarboxylicacids by oxidative cleavage of cyclic com-pounds are commercially significant; however,the oxidation of cyclohexane via cyclohexanol–cyclohexanone is the most important (!Adipic Acid). Similar processes are employedto convert cyclopentanol–cyclopentanone to

Figure 1. Manufacture of azelaic acid by ozonolysis of oleic acida) Ozone generator; b) Ozone absorber; c) Reactor; d) Distillation column; e) Extraction column; f) Distillation of theextractant; g) Flaking


glutaric acid, cycloheptanone to pimelic acid,and cyclododecanol–cyclododecanone to 1,12-dodecanedioic acid [12]. Figure 2 shows aprocess for the manufacture of 1,12-dodecane-dioic acid from cyclododecanol–cyclododeca-none [13].

The oxidation is carried out in a stirredreactor (b) fed continuously with nitric acidand cyclododecanol–cyclododecanone; ammo-nium vanadate is used as a catalyst. The nitricoxides formed during oxidation are recycled viathe condenser (d) and cooler (e). The reactionslurry passes to the postreaction stage and thento the crystallizer (g), in which most of the acidcrystallizes. The solids are filtered off and themother liquor is recycled to the reactor. Inindustrial-scale processes, selectivities towardthe acid of about 90 % are achieved.

Cyclic ethers can also be used as startingmaterials. Thus, pimelic acid is obtained from

potassium tetrahydrofurylpropionate [14] orfrom hydroxycyclohexanoic acid [15]. Hydrol-ysis of dihydropyran produces 5-hydroxypen-tanal, which is converted to glutaric acid bysubsequent oxidation with nitric acid [16].

Ozonolysis of Cyclic Olefins. Cyclic olefinscan be converted to dicarboxylic acids by ozo-nolysis and subsequent oxidative cleavage. Forexample, 1,12-dodecanedioic acid can beobtained by ozonolysis of cyclododecene (seeSection 2.4.9) [17].

Oxidation of Bifunctional Compounds.Dicarboxylic acids can be produced by oxida-tion of bifunctional compounds with HNO3 inthe presence of ammonium vanadate, withN2O4, or with oxygen in the presence of palla-dium on carbon. Diols are preferred asbifunctional starting materials. Well-knownexamples of this process are the syntheses ofpimelic acid from 1,7-heptanediol and of suc-cinic acid from 1,4-butanediol [18].

Nitrile Hydrolysis. Saponification of dinitrilesalso yields dicarboxylic acids. Thus, glutaricacid can be produced from glutarodinitrile,which is obtained by the reaction of 1,3-diha-lopropane with sodium cyanide. Saponificationof the nitrile group can take place concurrentlywith oxidation of a carbonyl group; e.g., 4-cyano-2,2-dimethylbutanal, obtained by theaddition of isobutanal to acrylonitrile, gives2,2-dimethylglutaric acid [19].

Hydrogenation. Hydrogenation of un-saturated dicarboxylic acids or their anhydridesproduces good yields of the correspondingsaturated compounds. Succinic acid is obtainedby this method from maleic acid or maleicanhydride [20].

Figure 2. Manufacture of 1,12-dodecanedioic acid fromcyclododecanol–cyclododecanonea) Scrubber; b) Reactor; c) Downstream reactor; d) Con-denser; e) Cooler; f) Separator; g) Crystallizer; h) Filter


Fermentation. Numerous alkane-based fer-mentation processes have been describedfor the manufacture of dicarboxylic acids[21]. However, these biotechnical processeshave not yet become standard commercialpractice.

2.3.3. Syntheses from Smaller Units

The main addition reactions leading todicarboxylic acids are variants of carbonyla-tion. Diolefins, dialcohols, and unsaturatedmonocarboxylic acids are used as starting mate-rials [22]. Reppe carbonylation of 1,6-hexane-diol produces suberic acid; C19 dicarboxylicacids are obtained from oleic acid [23].

The dimerization of monomethyl adipate tosebacic acid is an electrochemical processwhich has achieved commercial significance.Figure 3 illustrates this process [24].

The reaction takes place in three stages:

Esterification:

HOOC� CH2ð Þ4 � COOHþ CH3OH !HOOC� CH2ð Þ4 � COOCH3 þ H2O

Electrolysis:

�OOC� CH2ð Þ4 � COOCH3 � e� !1=2 CH3OOC� CH2ð Þ8 � COOCH3 þ CO2

Hþ þ e� ! 1=2 H2

Hydrolysis:

CH3OOC� CH2ð Þ8 � COOCH3 þ 2 H2O !HOOC� CH2ð Þ8 � COOHþ 2 CH3OH

In the first stage, adipic acid reacts withmethanol at 80 �C to formmonomethyl adipate.Ion exchangers containing sulfonic acid groupsare used as catalysts and also prevent the

Figure 3. Manufacture of sebacic acid by electrochemical dimerization of monomethyl adipatea) Mixing tank; b) Reaction column; c) Methanol stripper; d) Water stripper; e) Dimethyl adipate stripper; f) Adipic acidcutting column; g) Electrolyzer; h) Electrolyte tank; i) Decanter; J) Distillation column; k) Reactor; l) Mixing tank; m) Filter;n) Dehydrator; o) Prill tower


formation of byproducts such as cyclopenta-none. The monomethyl adipate is separated bydistillation.

In the second stage, the potassium salt ofmonomethyl adipate is dimerized electrolyti-cally either continuously or batchwise. Theelectrolyzer is equipped with bipolar electro-des. Electrolysis takes place at 50–60 �C. Aque-ous methanol is used as solvent, the H2Oconcentration being between 0.15 and 0.30%.The resulting dimethyl sebacate solution isdistilled, and unreacted potassium methyl adi-pate is returned to the electrolysis process.Dimethyl sebacate is purified by distillation.

In the third stage, dimethyl sebacate ishydrolyzed at 160–180 �C and a pressure ofabout 0.9 MPa (9 bar). Methanol is removed,and the crude sebacic acid is treated withactivated carbon and then dried.

The Wurtz synthesis can also be used [25]:

The reactivity of the methylene group inmalonic ester is exploited in many dicarboxylicacid syntheses (malonic ester synthesis; !Malonic Acid and Derivatives).

The Stetter dicarboxylic acid synthesis isanother important process [26]:

Long-chain dicarboxylic acids can be pre-pared in the following manner [27]:

Many processes used to manufacture mono-carboxylic acids are also suitable for the syn-thesis of dicarboxylic acids. This field has been

reviewed extensively [28] (! CarboxylicAcids, Aliphatic).

2.4. Individual Saturated DicarboxylicAcids

Dicarboxylic acids are used mainly as inter-mediates in the manufacture of esters and poly-amides. Esters derived from monofunctionalalcohols serve as plasticizers or lubricants.Polyesters are obtained by reaction with dia-lcohols. In addition, dicarboxylic acids areemployed in the manufacture of hydraulic flu-ids, agricultural chemicals, pharmaceuticals,dyes, complexing agents for heavy-metal salts,and lubricant additives (as metal salts).

2.4.1. Succinic Acid

Succinic acid is found in amber, in numerousplants (e.g., algae, lichens, rhubarb, and toma-toes), and in many lignites.

Production. A large number of syntheses areused to manufacture succinic acid. Hydrogena-tion of maleic acid, maleic anhydride, orfumaric acid produces good yields of succinicacid; the standard catalysts are Raney nickel[20], Cu, NiO, or CuZnCr [29], Pd��Al2O3

[30], Pd��CaCO3 [31], or Ni��diatomite[32]. 1,4-Butanediol can be oxidized to succinicacid in several ways: (1) with O2 in an aqueoussolution of an alkaline-earth hydroxide at90–110 �C in the presence of Pd��C; (2) byozonolysis in aqueous acetic acid; or (3) byreaction with N2O4 at low temperature [18].Succinic acid or its esters are also obtained byReppe carbonylation of ethylene glycol, cata-lyzed with RhCl3��pentachlorothiophenol[33]; Pd-catalyzed methoxycarbonylation ofethylene [34]; and carbonylation of acetylene,acrylic acid, dioxane, or b-propiolactone [35,36] (! Carbonylation).

Acid mixtures containing succinic acid areobtained in various oxidation processes. Exam-ples include the manufacture of adipic acid [2,37–39] (!Adipic Acid, Chap. 4); the oxidationof enanthic acid [40]; and the ozonolysis ofpalmitic acid [41].

The company BioAmber produces succinicacid fermentatively from glucose obtained by


hydrolysis of wheat starch. A 2000 t/a produc-tion facility went on-stream in Pomacle,France, in January 2010. A second productionfacility is planned in Sarnia, Ontario, Canada(joint venture of BioAmber and Mitsui) [42].

Succinic acid can also be obtained by phase-transfer-catalyzed reaction of 2-haloacetates[43], electrolytic dimerization of bromoaceticacid or ester [44], oxidation of 3-cyanopropanal[45], and fermentation of n-alkanes [46].

Uses. Succinic acid is used as a starting mate-rial in the manufacture of alkyd resins, dyes,pharmaceuticals, and pesticides. Reaction withglycols gives polyesters; esters formed byreaction with monoalcohols are important plas-ticizers and lubricants.

2.4.2. Glutaric Acid

Glutaric acid occurs in washings from fleeceand, together with malonic acid, in the juice ofunripened sugar beet.

Production. Glutaric acid is obtained fromcyclopentane by oxidation with oxygen andcobalt (III) catalysts [47, 48] or by ozonolysis[49]; and from cyclopentanol–cyclopentanoneby oxidation with oxygen and Co(CH3CO2)2,with potassium peroxide in benzene, or withN2O4 or nitric acid [12, 50–52]. Like succinicacid, glutaric acid is formed as a byproductduring oxidation of cyclohexanol–cyclohexa-none (! Adipic Acid).

Other production methods include reactionof malonic ester with acrylic acid ester [53, 54],carbonylation of g-butyrolactone [22], oxida-tion of 1,5-pentanediol with N2O4 [18], andoxidative cleavage of g-caprolactone [55].

Uses. The applications of glutaric acid, e.g., asan intermediate, are limited. Its use as a startingmaterial in the manufacture of maleic acid hasno commercial importance.

2.4.3. Dimethylglutaric Acids

2,2-Dimethylglutaric acid is manufacturedfrom dimethyl-g-butyrolactone by carbonyla-tion using HF��SbF5 as a catalyst or byreaction with formic acid in stronger acidssuch as H2SO4��SO3 [56, 57]. 4-Cyano-2,2-dimethylbutanal, which is obtained by addition

of isobutanal to acrylonitrile, can be convertedto the acid by oxidation of the formyl groupand subsequent hydrolysis of the nitrile group[19, 58].

2,2-Dimethylglutaric acid is used in themanufacture of diglycidyl esters (for coatingmaterials) [59], pyrethroids (for insecticidesand acaricides) [60], and antibiotics [61].

3,3-Dimethylglutaric acid [4839-46-7] is man-ufactured from isophorone by oxidation withH2O2 in the presence of concentrated sulfuricacid or by ozonolysis in methanolic solutionand subsequent oxidation with H2O2 [62]. Thisacid is used in the manufacture of pesticidesand lubricating oil additives.

2.4.4. Trimethyladipic Acid

Commercial trimethyladipic acid is a mixtureof ca. 40% 2,2,4-trimethyladipic acid and 60%2,4,4-trimethyladipic acid.

Production. Trimethyladipic acid is manufac-tured by oxidative cleavage of 3,3,5-trimethyl-cyclohexanol [116-02-9] (produced fromacetone) with 65% nitric acid at 50 �C [63].To separate the short-chain dicarboxylic acids,the mixture is heated to 180–250 �C andthe cyclic anhydrides formed are distilled off[64].

Uses. Trimethyladipic acid is used in theproduction of synthetic lubricating oils[65], polyesters [66], and polyamides [66],and in the modification of terephthalic acidesters [67].

2.4.5. Pimelic Acid

Pimelic acid is an oxidation product of fats.

Production. Pimelic acid can be manufacturedwith good selectivity by oxidation of cyclo-heptanone [502-42-1] (suberone) with N2O4

[12]. It is also obtained in a mixture with otherdicarboxylic acids by oxidative cleavage ofpalmitic acid [41]. Other manufacturing pro-cesses include oxidation of 1,7-heptanediol[68], carbonylation of e-caprolactone [22],and acid cleavage of tetrahydrosalicylic acidwith potassium hydroxide at 300 �C underpressure [15].


Uses. Pimelic acid has slight significance as astarting material in the manufacture of poly-esters and polyamides.

2.4.6. Suberic Acid

Suberic acid is formed from the action of nitricacid on cork.

Production. Suberic acid is manufactured byoxidation of cyclooctene with ozone–oxygen[49, 69] or with ozone��H2O2 [70]. The acid isformed together with other dicarboxylic acidsduring ozonolysis of palmitic acid [41] as wellas during cleavage of ricinoleic acid with nitricacid [71]. Other manufacturing processesinclude oxidation of cyclooctanol–cycloocta-none with N2O4 or HNO3 [12, 72], carbonyla-tion of 1,6-hexaneediol [73], and oxidativecleavage of 2-(cyclohexanon-2-yl)acetic acidethyl ester [26].

Uses. Suberic acid has been used in the manu-facture of mono- and diesters as well as poly-amides. Nylon 6,8 is obtained by reaction ofsuberic acid with hexamethylenediamine, andnylon 8,8 by reaction with octamethylenedi-amine. Polyamides of suberic acid withdiamines such as 1,3-bis(aminomethyl)ben-zene, 1,4(bisaminomethyl)cyclohexane, andbis(4-aminocyclohexyl)methane are also ofcommercial interest. Esters of suberic acidwith mono- and bifunctional alcohols areused as lubricants.

2.4.7. Azelaic Acid

Azelaic acid occurs in many natural substancescontaining long-chain fatty acids.

Production. Azelaic acid is obtained by oxida-tive cleavage of oleic acid with oxidants such asRuO4 [74] ; Cl2��RuO2 or Cl2��RuCl2 [75,76]; KMnO4 [77]; NaOCl��RuO4��OsO4 [78];and HNO3 [79]. The industrially most impor-tant process is the ozonolysis of oleic acid (seeSection 2.3.1) [9, 80, 81].

Other means of synthesizing azelaic acidinclude carbonylation of 1,5-cyclooctadiene[82], oxidation of 1,9-nonanedial with oxygen[83], oxidative cleavage of 2-cyanoethylcyclo-hexanone [84], and fermentation of pelargonic

acid [85]. A mixture of azelaic and otherdicarboxylic acids is obtained during ozonol-ysis of palmitic acid [41].

Uses. Monoesters of azelaic acid with 2-ethyl-hexanol are used as plasticizers. Mono- anddiesters with other alcohols act as hydraulicfluids and lubricating oils; their metal salts arerecommended as lubricating oil additives.Reaction with hexamethylenediamine leads tonylon 6,9, which is used as extruded film forfood packaging, as a coating for wire, and inthe electronics and automobile industries.Unsaturated polyesters are employed as resins,laminates, and adhesives.

2.4.8. Sebacic Acid

Production. The most important processesfor manufacturing sebacic acid are alkalinecleavage of ricinoleic acid (see Section 2.3.1)[86–89] and electrolytic dimerization of mono-methyl adipate (see Section 2.3.3) [90–92].2-Octanol is formed as a byproduct duringricinoleic acid cleavage. Other methods usedto manufacture sebacic acid are oxidation ofstearic acid by N2O4 [11], oxidation of 1,10-decanediol [18], and various fermentation pro-cesses [21, 93]. A mixture of sebacic acid andother dicarboxylic acids is formed during ozo-nolysis of palmitic acid [41]. Processes forpurifying sebacic acid are described in [94–96].

The C10 dicarboxylic acid mixture obtainedby dimerization of butadiene and subsequentreaction with CO2 is called isosebacic acid; itconsists of ca. 75% 2-ethylsuberic acid, 15%diethyladipic acid, and 10% sebacic acid.Because of the varying composition of differentproduction batches, this mixture has not beenable to gain a foothold in the market.

Uses. The polyamide nylon 6,10 obtained byreaction of sebacic acid with hexamethylenedi-amine no longer has great industrial signifi-cance. The sebacates of various oxo andstraight-chain alcohols are important plasticiz-ers. Their main characteristics are highmigration resistance and good low-temperatureresistance. The esters are also used ascomponents of lubricating oils and as diluents;because of their low toxicity they are importantcomponents of packaging films. Sebacic


acid-based alkyd resins are characterized bymarked flexibility.

2.4.9. 1,12-Dodecanedioic Acid

Over the past few years, 1,12-dodecanedioicacid has achieved industrial importance.

Production. The starting compound for indus-trial-scale production of 1,12-dodecanedioicacid is 1,5,9-cyclododecatriene (CDT), whichis obtained by trimerization of butadiene(! Cyclododecatriene, Cyclooctadiene, and4-Vinylcyclohexene). Cyclododecatriene canreact to form the acid by two different pro-cesses. In a three-stage reaction sequence,1,5,9-cyclododecatriene is first hydrogenatedto cyclododecane on nickel catalysts; cyclo-dodecane is then oxidized with oxygen or airto a cyclododecanol–cyclododecanone mix-ture; and this mixture is finally oxidized withnitric acid to 1,12-dodecanedioic acid (!Cyclododecanol, Cyclododecanone, and Laur-olactam) [97–101].

The second route consists of partial hydro-genation of 1,5,9-cyclododecatriene to cyclo-dodecene and subsequent oxidative ozonolyticcleavage to the acid [102–104]; ozonolysis ofcyclododecanol has also been described [17].

Other manufacturing processes such as thefermentation of n-dodecane [21, 105, 106] andthe oxidation of analogous mono- and diformylcompounds [107] have no industrial impor-tance. Processes for purifying the acid havebeen described [108–111].

Uses. 1,12-Dodecanedioic acid is used mainlyin manufacturing polyamides and polyesters.Reaction with hexamethylenediamine givesnylon 6,12; reaction with trans,trans-bis-(4-aminocyclohexyl)methane yields the poly-amide known as Qiana. 1,12-Dodecanedioicacid is also used for the manufacture of lubri-cating oils and plasticizers.

2.4.10. 1,13-Tridecanedioic Acid (BrassylicAcid)

Production. The most important raw materialfor the production of brassylic acid is erucicacid [112-86-7] (cis-13-docosenoic acid),which occurs in large quantities in the seedoil of rape, mustard, wallflower, and cress.Yields of 82��92% are obtained by ozonolysisof erucic acid in acetic acid and subsequentoxidation with oxygen [112, 113]. The byprod-uct, pelargonic acid, can be separated easily.Oxidative cleavage of erucic acid by reactionwith nitric acid is also possible [79].

CH3 � CH2ð Þ7 � CH ¼ CH� CH2ð Þ11 � COOH !CH3 � CH2ð Þ7 � COOHþ HOOC� CH2ð Þ11 � COOH

Fermentation of n-tridecane has been inves-tigated over the past few years, especially inJapan [114–118]; purification of the resultingacid is described in [119–122].

Uses. Brassylic acid is used in the manufactureof polyamides (nylon 13,13) and esters whichare employed as low-temperature plasticizersfor poly(vinyl chloride) (PVC) and as lubricantcomponents. It is also a starting material forsynthetic musk.

2.4.11. C19 Dicarboxylic Acids

Production. The composition of C19

dicarboxylic acid mixtures depends on themanufacturing process. Three processes, basedon oleic acid or oleic acid esters, are usedindustrially: (1) Reppe carbonylation catalyzedby Ni(CO)4 or metal complexes such asPdCl2��triphenylphosphine; (2) Koch reactionin concentrated sulfuric acid at 10–20 �C [23,123, 124] or with HF catalysis at 30 �C [125];and (3) hydroformylation. Hydroformylationgives a mixture of isomeric formylstearates,


which are subsequently oxidized with air oroxygen. Oxidation takes place in an aqueousemulsion at 20–25 �C in the presence of cal-cium acetate or manganese naphthenate catalyst[126, 127]. Potassium permanganate [128–130]or potassium dichromate [129, 130] can also beused as the oxidizing agent.

Uses. Esters of C19 dicarboxylic acids are usedas plasticizers for PVC. The esterification rateof the terminal carboxyl group is considerablyhigher than that of the central group. Thisallows selective synthesis of mixed esters.

The C19 dicarboxylic acids are also used asstarting materials in the production of polya-mides, epoxy resins, unsaturated polyester res-ins, lubricants, and adhesives.

3. Unsaturated Dicarboxylic Acids

The most important derivative of unsaturateddicarboxylic acids is maleic anhydride (!Maleic and Fumaric Acids). Unsaturated C36

dicarboxylic acids containing cyclic structures,which are known as dimer acids, also havesome industrial significance.

3.1. Physical Properties

Table 2 lists the most important physical prop-erties of some unsaturated aliphatic dicarboxylicacids. The lower members of the series arecolorless, crystalline substances at room temper-ature; the dimer acids, which are commerciallyavailable as isomeric mixtures, are viscousliquids at 25 �C. Melting point, solubility inwater, and dissociation constants of the lowerhomologues are influenced byconfiguration. Forexample, the melting points of fumaric andmesaconic acid (trans) are considerably higherthan those of the cis isomers maleic and citra-conic acid, respectively; the trans isomers arealso much less water soluble and less acidic. Anindication of the higher stability of the trans formis the higher heat of combustion of maleic acidcompared with fumaric acid.

3.2. Chemical Properties

The chemical behavior of unsaturated aliphaticdicarboxylic acids is determined primarily by

the two carboxyl groups (see Section 2.2) andthe olefinic double bond. Reactions of thecarboxyl groups can also be influenced bythe olefinic bond. For example, when maleicor citraconic acid is heated above 100 �C, wateris split off, and maleic or citraconic anhydride isobtained (! Maleic and Fumaric Acids).Fumaric acid, however, forms no anhydride;above 230 �C, decomposition occurs andmaleic anhydride, water, and an appreciableamount of residue are formed.

Addition of halogen to the carbon–carbondouble bond yields dihalodicarboxylic acids;reaction with ozone gives formylcarboxylicacids; and hydroxydicarboxylic acids areformed by addition of water. Catalytic hydro-genation leads to saturated dicarboxylic acids;the cis isomers generally react much morequickly than the trans isomers.

The Diels–Alder reaction of maleic anhy-dride with conjugated dienes is used bothindustrially and in preparative organic chem-istry [131]; for example, tetrahydrophthalicanhydride is formed by reaction withbutadiene:

Comprehensive information on reactionswith unsaturated dicarboxylic acids can befound in [132].

3.3. Production

Only a few processes are used industrially forthe production of unsaturated dicarboxylicacids:

1. Oxidation of hydrocarbons (maleic anhy-dride from benzene and C4 hydrocarbonssuch as n-butane and n-butene; see !Maleic and Fumaric Acids)

2. Diels–Alder reaction of unsaturated acids(dimer acids from oleic or linoleic acid; seeSection 3.4.2)

3. Fermentation (itaconic acid)


Tab

le2.

Physicalproperties

ofunsaturateddicarboxylicacids


3.4. Individual UnsaturatedDicarboxylic Acids

Unsaturated dicarboxylic acids are used mainlyto manufacture unsaturated polyester resins,copolymers, or polyamides, and as intermedi-ates in the synthesis of herbicides, insecticides,fungicides, surfactants, lubricants, andplasticizers.

Maleic anhydride is also employed as astarting material for the manufacture of DL-tartaric acid, DL-malic acid, glyoxylic acid,and tetrahydrophthalic anhydride, as wellas g-butyrolactone, 1,4-butanediol, andtetrahydrofuran.

3.4.1. Itaconic Acid

Itaconic acid (2-methylenebutanedioic acid) issoluble in water; moderately soluble in chloro-form, benzene, and ligroin; and slightly solublein ether. When distilled at normal pressure,itaconic acid or itaconic anhydride yields cit-raconic anhydride.

Production. Itaconic acid is produced by fer-mentation [133–139]. A mixture of itaconicacid, citraconic acid, and citraconic anhydrideis obtained by reaction of succinic anhydridewith formaldehyde at 200–500 �C in the pres-ence of alkali or alkaline-earth hydroxides[140]; SiO2��Al2O3 or SiO2��MgO can alsobe used as catalysts [141]. Other methodsinvolve carbonylation of propargyl chloridewith metal carbonyl catalysts [142] and thermaldecomposition of citric acid.

Uses. Itaconic acid can be used as acomonomer and in the separation of triorgano-phosphine mixtures [143].

3.4.2. Dimer Acids

The only higher dicarboxylic acids of commer-cial importance are unsaturated cyclic C36

dicarboxylic acids known as dimer acids. Themain difference among various standard pro-prietary products is the content of trimer com-pounds; the ratio of dimer to trimer acids canvary from 36 : 1 to about 0.7 : 1 [144]. Thecomposition of dimer acids depends to a large

degree on the feed materials and the manufac-turing process.

Production. Dimer acids are produced by inter-molecular condensation of unsaturated C18

carboxylic acids or their esters. Tall oil fattyacids are the main feed materials, but oleicand linoleic acids can also be used. The reactionis conducted preferably in the presence ofspecial aluminum silicates (montmorillonites)at 190–240 �C; thermal dimerization at270–290 �C is also possible [145–148]. Numer-ous catalyst modifications such as addition ofalkali, amines, or sulfonic acid halides aredescribed in the literature. A summary of themanufacturing processes for dimer acids can befound in [152–154]. Diels–Alder and free-radi-cal reactions have been suggested as mecha-nisms for the thermal dimerization [149]; whenaluminum silicates are used, ionic intermedi-ates may be formed. Commercial processesyield mixtures of dimer acids, higher polycar-boxylic acids, and various isomeric monomeracids, which are separated by distillation usingfilm evaporators. After removal of the mono-mer acid fraction and the polycarboxylic acids,the remaining acids can be separated by furtherdistillation into dimer and trimer acids. Figure 4shows some dimer acids found in commercialmixtures. Investigations of the structu res ofdimer acids can be found in [150, 151].

Figure 4. Dimer acids found in commercial mixtures


Uses. The dimer acids produced on an indus-trial scale are used in the manufacture of poly-amides, polyesters, epoxy resins, lubricants,plasticizers, and pesticides [155–158].

4. Quality Specifications andAnalysis

Quality control of dicarboxylic acids covers thedetermination of content, melting point, color,traces of heavy metals, and solubility in wateror other solvents. High purity is generallydemanded of dicarboxylic acids.

The content of dicarboxylic acids is usuallydetermined by acidimetric titration. Specificregulations exist for properties; for regulationsconcerning dimer acids, see [159, 160]. Speci-fications may include condition, color, content,and ash. Melting point, density, refractiveindex, water content, steam pressure, specificheat, dissociation constants, and solubility inwater and other solvents are also oftendetermined.

The most important qualitative or quantita-tive analytical method used industrially is gaschromatography. Dicarboxylic acids are firstconverted into their esters (preferably methylesters) because free acids generally undergoundesirable secondary reactions during chro-matography. Both packed columns and capil-lary columns with stationary liquids of differentpolarities are used. Calcined kieselguhr is themost common carrier material. Other chro-matographic methods such as HPLC, paperand thin-layer chromatography, and gel chro-matography are also widely employed.

Alkalimetric titration is commonly used tomonitor the different production steps and toidentify pure dicarboxylic acids or their mix-tures. In the absence of other reducing agents,oxalic acid is determined by titration withpotassium permanganate. Crystalline deriva-tives such as phenacyl esters and amides areparticularly suitable for chemical determinationof dicarboxylic acids.

With infrared spectroscopy, dicarboxylicacids can be detected by the intense carbonylstretching frequency in the range of 1650–1740cm�1. In the 1H-NMR spectrum, the hydroxylproton signals can be found at d ¼ 10–13 ppm;the signals for the methylene groups of malonic

and succinic acids are around 3.4 and 2.6 ppm,respectively. In the 13C-NMR spectrum, theabsorption range of the carboxyl carbon atomis around d ¼ 160–180 ppm.

For further details on analysis, see [159, 161].

5. Storage, Transportation, andHandling

At room temperature, straight-chain dicar-boxylic acids are solid compounds thatare delivered and stored as crystals or —particularly if a melt or distillation is used torecover the pure substance — as flakes.

Dicarboxylic acids are stored and trans-ported in drums made of plastic-coated steel,stainless steel, or aluminum. Polyethylene-lined paper sacks are also used. These acidsare hygroscopic and should be stored in cool,dry rooms to avoid clumping. Shipping regula-tions and hazard classification for dicarboxylicacids depend on the specific properties of thecompounds such as flash point, decompositiontemperature, water solubility, toxicity, and igni-tion temperature.

Aliphatic dicarboxylic acids are local irri-tants, especially to the mucous membranes; thiseffect decreases with increasing chain length.Oxalic acid is absorbed readily by the outerlayers of the skin and can upset the body’scalcium balance through the formation of cal-cium oxalate. Therefore, gloves and safetyglasses must be worn when dicarboxylic acidsare handled. To avoid dust that can damagehealth, dicarboxylic acids are normally sup-plied in the form of flakes or laminatedmoldings.

Waste gases from dicarboxylic acid produc-tion facilities are generally drawn off at acentral point and fed into a combustion cham-ber. The wastewater is subjected to chemicaland biological treatment.

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Further Reading

M. N. Belgacem, A. Gandini (eds.): Monomers, Polymers and

Composites from Renewable Resources, Elsevier, Amsterdam2008.

F. Cavani, G. Centi, S. Perathoner, F. Triffir�o (eds.): SustainableIndustrial Processes, Wiley-VCH, Weinheim 2009.

A. J. Dijkstra, R. J. Hamilton, W. Hamm (eds.): Trans Fatty Acids,Blackwell, Oxford, UK 2008.

J. Otera, J. Nishikido (eds.): Esterification, 2nd ed., Wiley-VCH,Weinheim 2010.

R. D. Schmid, V. B. Urlacher (eds.): Modern Biooxidation, Wiley-VCH, Weinheim 2007.


ullmann's encyclopedia of industrial chemistry || dicarboxylic acids, aliphatic

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