CHAPTER 1

Introduction to Plant Growth Regulators

ABSTRACT

Heterocycles are playing vital role in various biological activities in regular life. They

are also used in agrochemicals as pesticides and plant growth regulators. Present work

highlights the study about heterocycles, particularly as plant growth regulators; their

types, discovery, biosynthesis, functions, roles, as herbicides; their mode of actions

and the set of some commercial products.

Key words: Heterocycles, agrochemicals, plant growth regulators, herbicides.

CHAPTER 1 2

1.1 Introduction
India is an agricultural country with about 40 million hectares of land under

cultivation. Over 65-70% of country‟s population lives in rural areas where majority

of people are belong to farming communities.

Obviously, the soil, climate and topography vary from region to region and

although intensive and multiple cropping systems are practiced and proper irrigation

facilities are provided, still we have less crop yield. On other hand we have about 60-

70% of our land is rain fed, due to lack of water or insufficient resources of water, and

here there is a problem of stunting crop and hence, here also we have less crop yield.

Apart from these, there are various stresses i.e. water stress, high temperature, cold,

heavy rainfall, etc. faced by crops, which are also responsible for less crop yield.

In our country farmers are using pesticides to increase their production in

following pattern shown in figure 1 but, even then they are not getting that much

production or crop yield. The reason behind the less production is not known to them,

they are not much aware about the plant growth regulators and their role in plant

growth. Plant Growth Regulator (PGR) is one of the classes of agrochemicals.

Figure 1: Pesticides used pattern of India

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 3

1.2 Agrochemicals

Agrochemicals are the chemical substances which protect, preserve and

regulate the growth of plants, thus improving the crop yield [1].

Classification of Agrochemicals

They are classified mainly as follows,

Figure 2: Classification of agrochemicals

1.2.1 Pesticides

These are the chemicals or mixture of chemicals which are used to control,

mitigate or kill the pest organisms.

Examples- Insecticides (imidacloprid), fungicides (carbendazim), nematicides

(triazophos), rodenticides (warfarin), etc.

1.2.2 Fertilizers

Fertilizers are inorganic materials which can supply plant nutrient in available

form, they are having high analytical value and definite composition.

Examples- Nitrogenous fertilizers (urea, ammonium sulphate), phosphate fertilizers

(single/triple super phosphate) potassic fertilizers (murate of potash), macronutrients

(Ca, Mg, O, C), micronutrients (Zn, Mn, Cu, Fe, Mo, S, etc),

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 4

1.2.3 Plant Growth Regulators (PGRs)

“Plant growth regulators usually are defined as organic compounds, other than

nutrients, that in small concentrations, affect the physiological processes of plants”. In

practical purpose, they are defined as either natural or synthetic compounds that are

applied directly to plant to alter its life processes/structure in some beneficial way so

as to enhance yield, improve quality and facilitate harvesting. When herbicides are

applied to induce a specific beneficial change, then they are considered as plant

growth regulators [2]. If the compound is produced within the plant it is called a plant

hormone. The term "hormone" is derived from a Greek word meaning “to arouse or

stimulate or enhance an activity" [3].

A plant growth regulator is defined by Environmental Protection Agency

(EPA) as “any substance or mixtures of substances intended, through physiological

action, to accelerate or retard the rate of growth or maturation or otherwise alter the

behavior of plants. Additionally, plant growth regulators are characterized by their

low rates of application, while the high application rates of the same compounds often

are considered as herbicidal”. Plant hormones are produced naturally by plants and

are essential for regulating their own growth. They act by controlling or modifying

plant growth processes, such as formation of leaves and flowers, elongation of stems,

development and ripening of fruits.

In modern agriculture practices, people have established the benefits of

extending the use of plant hormones to regulate growth of other plants. When natural

or synthetic substances are used in this manner, they are called Plant Growth

Regulators.

The application of plant growth regulators in agriculture has started in 1930 in

United States. Ethylene, a naturally occurring substance, is one of the first plant

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 5

growth regulators being discovered and used successfully for enhancing flower

production in pineapple [4]. Its toxic effects to human beings are low. Synthetic

substances that mimic such naturally occurring plant hormones were also produced,

since then the use of plant growth regulators has been growing significantly and

becoming a major component in modern agriculture.

Classification of Plant Hormones/Growth Regulators

They are classified as auxins, gibberellins, cytokinins, ethylene and abscisic acid.

Auxins

Auxin is the first plant hormone/growth substance discovered. The term comes

from the Greek word, auxein means "to grow". Compounds are generally considered

as auxins if they are synthesized by the plant and have similar activity to Indole-3-

acetic acid (IAA) [5,6].

Discovery of Auxins

Charles Darwin was the first scientist who performed early auxin experiments

on canary grass (Phalaris canariensis) coleoptiles. He observed the effects of a

hypothetical substance modulating plant shoot elongation to allow tropic growth

toward light [7].

IAA is the major auxin involved in many of the physiological processes in

plants [5]. It was discovered by Salkowski in 1885 in fermentation media [8].

In 1926, a graduate student F. Went from Holland, who isolated a plant growth

substance by placing agar blocks under coleoptile tip for some time, then removing

and placing them on decapitated Avena stems. After placement of the agar, the stems

resumed growth [9]. In 1928, Went developed a method to quantify this growth

substance. From which he concluded that the curvatures of stems were proportional to

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 6

the amount of growth substance in the agar block [10]. This test is known as the avena

curvature test (Figure 3). Kogl and Haagen-Smit purified the compound auxentriolic

acid (auxin A) from human urine in 1931[11]. After that Kogl isolated other

compound from urine, which was IAA, the same was primarily discovered by

Salkowski in 1885. Finally in 1954 plant physiologists committee was set up to

characterize the group auxin.

Figure 3: Avena curvature test

Biosynthesis of Auxin [12,13]

IAA is similar to the amino acid tryptophan which is generally accepted to be the

precursor molecule from which IAA is derived by different pathways.

Tryptophan is converted to indoleacetaldoxime through decarboxylation and

then converted to indoleacetonitrile by a dehydration reaction. The final step involves

oxidation of indoleacetonitrile results in indoleacetic acid.

Tryptophan is converted to indolepyruvic acid through a transamination

reaction. Indolepyruvic acid is then converted to indoleacetaldehyde by a

decarboxylation reaction; finally oxidation of indoleacetaldehyde, resulting in

indoleacetic acid.

Tryptophan undergoes decarboxylation resulting in tryptamine. Tryptamine is

then oxidized and deaminated to produce indoleacetaldehyde. This molecule is further

oxidized to produce indoleacetic acid.

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 7

In the bacterial biosynthetic pathway monooxygenase converts tryptophan to

indoleacetamide and then it is converted to indoleacetic acid by hydrolysis.

NH2

COOH Monooxygenase
N Traptophan
H
Decarboxylase
Transaminase

NH2
NOH COOH N
N N H Traptamine
H H Indole-3-pyruvic acid
Indole-3-acetaldoxime
Decarboxylase Oxydase

O
H
N N Indole-3-acetaldehyde
N H NH2
H
Nitrilase Dehydrogenase N
Indole-3-acetonitrle H
Indole-3-acetamide
O Hydrolase

OH
N
H
Indole-3-acetic acid
Figure 4: Biosynthetic pathways of IAA

Functions of Auxin [14]

The following are some of the responses that auxin is known to cause,
Stimulates cell loosening, expansion and elongation

Initiation of adventitious roots on stem cuttings

Lateral root development in tissue culture

Stimulates differentiation of phloem and xylem

Stimulation of abscission (young fruits) or delay of abscission

Stimulates cell division in tissue culture in combination with cytokinins

Mediates the tropistic response of bending in response to gravity and light

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 8

Gibberellins

Gibberellins are synthesized in young tissues of the shoots, uncertainly in

roots and also in the developing seeds. There are also some evidences that leaves may

be the source of some biosynthesis [15].

Discovery of Gibberellins

A Japanese scientist E. Kurosawa in 1926 found that some of the rice

seedlings grow taller than others. He discovered the seedlings to be infected by the

pathogenic fungus Gibberella fujikuroi [16]. In his work he found that the rice plant

diseases bakanae (foolish seedling) caused by this fungus is having some metabolites

that might be responsible for the stimulated growth of seedlings. In 1935, an

agricultural chemist T. Yabuta isolated a non-crystalline material from the similar

type of culture that he named as “gibberellins” [17]. After that, in 1938 he was

succeeded in isolating pure pale yellow crystals [18]. In 1950, it was identified as

hormones of non-infected plants [19]. All gibberellins are derived from the ent-

gibberellane skeleton. The gibberellins are named GA1, GA2, GA3, ........, GAn in their

order of discovery. Gibberellic acid -GA3, was first structurally characterised

gibberellin. There are at present 136 GAs that have been identified from plants, fungi

and bacteria [20]. They have either 19 or 20 carbon atoms into either four or five ring

systems.

Biosynthesis of Gibberellins [21,22,23]

Acetyl CoA molecules are oxidized to produce mevalonic acid and CoA

molecules. Then Mevalonic acid is phosphorylated by ATP, followed by

decarboxylation to form isopentyl pyrophosphate. Four of these molecules react to

form geranylgeranyl pyrophosphate which serves as the donor for all GA carbons.

This compound is converted to copalylpyrophosphate (2 ring systems) then converted

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 9

to ent-kaurene (4 ring systems). Successive oxidations give ent-kaurenol (alcohol),

ent-kaurenal (aldehyde), ent-kaurenoic acid, ent-7a-hydroxy kaurenoic acid to form

the aldehyde of GA12 and it is the 1st true gibberellane (20 carbons ring system). From

the aldehyde -GA12 can make both 19 and 20 carbon gibberellins and the other

compounds arise by different mechanisms.

The primary precursor for formation of gibberellin is acetate.

O HO O HO
Acetate + CoA Acetyl CoA
HO OH HO OPP
Mevalonic acid Mevalonic acid
pyrophosphate

OPP

OPP OPP
GGPP GPP Isopentenyl
pyrophosphate

OPP

Copalyl CH2OH CHO

pyrophosphate ent-Kaurene ent-Kaurenol ent-Kaurenal

CO2H CHO OH
CO2H CO2H CO2H
CO2H
Gibberellin (GA12) Aldehyde of GA12 ent-7a-Hydroxy kaurenoic acid ent-Kaurenoic acid

Figure 5: Biosynthetic pathway of gibberellins

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 10

Functions of Gibberellins [23]

Physiological processes stimulated by active gibberellins depend on their types.

Stimulate cell elongation in stem

Breaks seed dormancy in some plants which requires light for germination

Stimulates alpha-amylase production in germinating cereal grains

Stimulates bolting/flowering in response to long days

Delay senescence in leaves and also in citrus fruits

Induces maleness in dioecious flowers

Play a role in development of seedless fruit (parthenocarpic).

Cytokinins

In Cytokinin, cyto = cell + kinin = division, i.e. meaning is cell division.

Cytokinin is also called as cytokine. These are the compounds resembling with

adenine (aminopurine) which stimulates cell division.

Discovery of Cytokinins

In 1913, G. Haberlandt found that phloem from various plants had an ability to

stimulate cell division in wounded potato tubers. This study implies the existence of

soluble factor(s) that could promote cell division in plant [24]. Then after the

beneficial effects of plant extracts, including coconut milk, the liquid endosperm from

immature fruits, on plant tissue cultures was first shown by Van Overbeek in 1941

[25]. In 1950, during the work primarily in F. Skoog‟s laboratory by C. Miller, he

identified cytokinin as a factor that promotes cell division in plant [24]. These

findings finally led to the isolation of kinetin from old autoclaved herring sperm DNA

by C. Miller in 1955 [26], while fresh DNA preparations displayed no effect at all. In

the end Kinetin (purine derivative, 6-furfurylaminopurine) was identified as the

effective substance, further it was synthesized in 1956 [27]. Kinetin and several other

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 11

similar molecules were initially named as kinin, in order to avoid confusion which

was later changed to cytokinin. After the discovery of kinetin and other cytokinins,

Skoog and Miller in 1957 demonstrated the hormonal (auxin/cytokinin) regulation of

plant morphogenesis. This controlled the formation of shoots/roots in callus tissues

culture [28]. It is an exact and an important consideration in understanding plant

morphogenesis, micropropagation and regeneration of plants in tissue culture. In

1963, zeatin was isolated from immature sweet corn seeds (Zea mays) by D. S.

Letham; it was the first natural cytokinin derived from plant that has kinetin-like

activity [29]. After all, in 2001 cytokinin biosynthesis in plants was established by

Japanese researchers [30].

Biosynthesis of Cytokinins [31,32]

Generally, cytokinins are found in more concentrations in meristematic tissues and in

growing parts. They are synthesized in roots and translocated to shoots acropetally via

xylem; they are synthesized as follows,

There two pathways, methylerythritol phosphate (MEP)-pathway and

mevalonic acid (MVA)-pathway both are converted to dimethylallyl pyrophosphate

(DMAPP) and which reacts with adenosine diphospate (ADP)/ATP in presence of

isopentenyl trasferase then, converted to isopentenyl-adenosine-diphosphate

(iPDP)/iPTP, zeatin riboside-diphosphate (ZDP)/ZTP, dihydrozeatin riboside-

diphosphate (DHZDP)/DHZTP and to isopentenyl-adenosine-monophosphate (iPMP),

zeatin riboside-monophosphate (ZMP), dihydrozeatin riboside-monophosphate

(DHZMP) and to isopentenyl adenosine (iPA), zeatin riboside (ZR), dihydrozeatin

riboside (DHZR) and to isopentenyl adenine (iP), zeatin (Z), dihydrozeatin (DHZ),

respectively and also to cis-zeatin.

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 12

Methylerythritol phosphate
MEP
Mevalonic acid
MVA

Dimethylallyl pyrophosphate Adenosinediphosphate

DMAPP ADP (or ATP)

Isopentenyl Transferase

Isopentenyl-adenosine- Isopentenyl-adenosine Isopentenyl Isopentenyl

diphosphate iPDP (or iPTP) -monophosphate iPMP adenosine iPA adenine iP

zeatin-riboside- Zeatin-riboside Zeatin riboside Zeatin cis-Zeatin

diphosphate -monophosphate ZMP ZR Z
ZDP (or ZTP)

Dihydrozeatin-riboside- Dihydrozeatin-riboside Dihydrozeatin

diphosphate Dihydrozeatin
-monophosphate DHZMP riboside DHZR DHZ
DHZDP (or DHZTP)

Figure 6: Biosynthetic pathways of zeatin

Functions of Cytokinins [30,33]

Physiological processes stimulated by cytokinins,

Stimulates cell division

Activates metabolite attraction (sink effect)

Retardation of senescence (at low concentrations)

Induction of apoptosis (at high concentrations)

Stimulates morphogenesis in tissue culture

Stimulates the growth of lateral buds and leaf expansion by cell division &
enlargement

Stimulation of chlorophyll synthesis that causes the conversion of etioplasts

into chloroplasts

Enhance stomatal opening in some plants

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 13

Ethylene

Ethylene has simplest structure among all the plant hormones. It is a gaseous

compound that has effects like an abscisic acid.

Discovery of Ethylene

In 1901, D. Neljubow, a Russian student at the St. Petersburg Botanical

Institute, found that the pea seedlings grown in dark show abnormal horizontal growth

of stems. But when they were placed outside in fresh air, they resumed normal

growth. Then he concluded that the ethylene gas, generated by gas lamps in the

laboratory, had caused the abnormal growth [34]. In 1917 Doubt studied different

types of responses of ethylene gas on several plant tissues. She noted several

responses that were: leaf scars and drop, epinasty of petioles, etc. [35,36]. R. Gane in

1934 reported that plants synthesize ethylene [37]. Afterwards in 1935 Crocker

considered ethylene as a plant hormone [38]. When gas chromatography was

introduced in 1959, the importance and physiological significance of ethylene as a

plant growth regulator was recognized [39].

Biosynthesis of Ethylene [40,41]

Ethylene is produced by methionine in all higher plants essentially in all tissues.

Ethylene production varies with type of tissue, plant species and stage. The

mechanism is as follows,

ATP played a vital role in the synthesis of ethylene from methionine. ATP and

water are added to methionine resulting in loss of the three phosphates and formation

of S-adenosyl methionine (SAM). Further, it is converted to 1-amino-cyclopropane-1-

carboxylic acid by ACC-synthase then to ethylene by ACC-oxidase.

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 14

NH3

NH3 H 3C
S COO H 3N COO
ATP, H2O ACC Synthase
H3 C
S COO O
OH
Methionine 1-amino-cyclopropane
Adenine -1-carboxylic acid
OH
S-adenosyl methionine ACC Oxidase
1/2 O2

H H
HCN
H H H2 O
Ethylene CO2

Figure 7: Biosynthetic pathway of ethylene

Functions of Ethylene [42]

Ethylene is known to affect the following plant processes,

Induce shoot and root growth and also differentiation

Stimulates the growth/release of dormancy

Stimulates leaf and fruit abscission

Stimulates Bromiliad flower induction

Induction of femaleness in dioecious flowers

Stimulates flower senescence, leaf senescence and flower opening

Stimulates fruit ripening

Abscisic Acid

Abscisic acid (ABA) controls several physiological processes in plants and

best known for regulatory role in abiotic stresses like drought and high salinity. It

promotes stomatal closing by which plants enable to adapt to water stress (desiccation

tolerance). It also controls seed germination, vegetative growth and bud dormancy

[43].

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 15

Discovery of Abscisic Acid

In 1963, F. Addicott and his associates first identified and characterized the

abscisic acid that is responsible for the abscission of fruits. They isolated two

compounds and called abscisin I & abscisin II [44,45]. Abscisin II is presently known

as abscisic acid (ABA).

Biosynthesis of Abscisic Acid [46,47]

There are following two pathways of ABA biosynthesis.

ABA is synthesized by higher plants from carotenoid precursors. Carotenoids

(Violaxanthin, C40) are involved in photosynthesis; they are cleaved to xanthoxin

(C15) and C25 derivative in the plastid by the enzyme (dioxygenase). Then xanthoxin

is converted to AB-aldehyde (abscisic aldehyde) then to ABA by oxidase enzyme

respectively, this is the major route. If aldehyde oxidation is blocked then ABA is

produced via AB-alcohol (abscisic alcohol) route. If AB-aldehyde oxidase uses

xanthoxin as an alternative substrate, then xanthoxic acid might be an intermediate

and this is the minor route.

ABA is a sesquiterpenoid produced via the isoprenoid pathway in chloroplasts

by mevalonate, through the intermediates isopentenyl, geranyl and farsenyl

pyrophosphate.

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 16

9-cis-Violaxanthin OH
O

O2 Cleavage enzyme

OH

O
CHO
HO
Xanthoxin
Mevalonate

Isopentenyl
Xanthoxic pyrophosphate
acid
OH
CHO
O
AB-aldehyde
Geranyl
pyrophosphate
AB-alcohol

Farnesyl
OH
COOH pyrophosphate
O
ABA

Figure 8: Biosynthetic pathways of ABA

Functions of Abscisic Acid [45,48]
The physiological responses made by abscisic acid,

Stimulates the closure of stomata

Stress responses especially to water deficiency

Induces seed and bud dormancy

Induces seed to synthesize, storage proteins

Inhibits shoot growth but does not have much affects on roots

Inhibits the synthesis of alpha-amylase stimulated by gibberellins

Induce some effects on induction and maintenance of dormancy

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 17

1.3 Important Roles of Plant Growth Regulators

Germination: Germination is the beginning of growth of a plant from a previously

dormant seed which contains the embryo [49]. Dormancy is the phase in which

biological activities are at rest/suspended; dormancy can be broken by external

application of PGRs like auxins and GAs.

Rooting: Root promoting chemicals are referred to as “rooting hormones”, they are

often used on stem cuttings using different methods. Auxins are used as rooting

hormones [50].

Callus Induction: In plant tissue culture, cytokinins and auxins are used for callus

induction from explants [51,52].

Growth Inhibitor: Inhibit means to „stop‟ the growth. It stops apical growth and

promotes lateral bud growth, which results in branched and more compact plants with

an increased number of flowers and fruits [53]. These chemicals are also used in long

storage of suckers.

Growth Retardant: Retard means to „slow‟ the growth. These chemicals regulate

shoot growth of plant resulting in a sturdier and more compact plant with improved

color [54].

Thinner: Thinning is the process of reducing denseness of flowers/fruits, which helps

to increase fruit size, quality and maintain tree structure. To maximize crop quality

and yield, load must be estimated for the optimal crop, the maximum number of fruits

to be retained after thinning [55].

Chemical Pruning: Pruning is a process of restricting of plant height. It is also

known as pinching or suckering. Pruning promotes the growth of new branches.

Generally growth inhibitors are used for chemical pruning [56,57].

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 18

Defoliant: Any substance or mixture of substances intended for causing the leaves or

foliage to drop from a plant, with or without causing abscission [58].

Defoliation is the method of treatment that causes only the leaves of a plant to

abscise or fall off. These are applied to cotton to improve and facilitate mechanical

harvesting [59].

Desiccant: Any substance or mixture of substances intended for artificially

accelerating drying of plant tissues [58].

Desiccation is the method of treatment that rapidly kills the leaves, which are

used for purpose similar to the uses of defoliants, but desiccant causes green foliage to

lose water; it is a hastened drying process that results in removal of leaves [59].

Fruit Ripener: Ripening is the final stage of fruit development, which involves series

of physiological and biochemical events mainly to change colour, texture, aroma and

flavor that makes fruit attractive & tasty. Fruit ripeners are the substances which can

hasten ripening process and artificially ripen fruits for commercial purpose [60].

General Mode of Entry of PGR/Hormone into Plant Cell

Following figure describes the general mode, from introduction to cellular

response of PGR/Hormone into plant cell.

Figure 9: General mode of entry of PGR/hormone into plant cell

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 19

1.4 Herbicides [61]

Herbicides belong to a group of chemicals known as pesticides.

Herbicide or Weedicide is any chemical substance that is used to specifically kill

plants.

Weed: Weed or Herb is the plant out of place or unwanted.

The weed grows nearby the crop; it competes with the main crop for space, macro and

micronutrients, water, sunlight etc.

1.4.1 Mode of Action of Herbicides

Herbicide‟s mode of action is the biochemical mechanism by which it kills

plants. Most of the herbicides kill plants by disrupting one or more of metabolic

processes. Some disrupt the cell membranes, some leak out cell membranes

specifically without disrupting other metabolic processes. Whole groups of plants are

not susceptible to certain herbicides because they have slightly different enzymes and

different biochemical pathways [62].

Amino Acid Synthesis Inhibitors [62,63]

The herbicide blocks the action of the enzyme 5-enolpyruvylshikimate-3-

phosphate (EPSP) synthase, which is responsible for synthesis of certain aromatic

amino acids such as tryptophan phenylalanine and tyrosine, which are required for

protein synthesis and are necessary for plant growth and development. Hence this is

the reason behind the death of plant.

Photosynthesis Inhibitors [62,64]

There are two types of photosynthesis inhibitors.

In first type that inhibits the transfer of electrons in photosystem (PS) II that is

from QA to QB in the chloroplast thylakoid membranes, due to the binding of

herbicide molecule to the protein (D1) protein at the QB binding niche. The electrons

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 20

are transferred through a series of reactions to other reactive toxic compounds. They

cause disruption of cell membranes, chloroplast swelling, membrane leakage and

finally cellular destruction.

In second type, the herbicide accepts electrons from Photosystem (PS) I and

thereafter generates hydroxyl radicals, which are extremely reactive and rapidly

destroy unsaturated lipids, fatty acids and chlorophyll. It also destroys cell membrane

so that the membrane “leaks”, thereby causing wilting of leaf and desiccation up to

plant death.

Mitosis Inhibitors [62]

The herbicide, that may acts as a plant growth regulator. This term sometimes

referred to as a “dormancy enforcer,” but the exact mechanism of action has not been

yet known. If applied to deciduous plant before two months of leaf drop, afterwards

the plant fails to leaf out and develop bud. The plants often die due to the lack of

photosynthesis. If applied to susceptible, non-deciduous plants, they die soon after

application.

Lipid Biosynthesis Inhibitors [62,65]

The herbicides inhibit synthesis of enzyme which helps in lipid synthesis.

They also inhibit acetyl CoA carboxylase enzyme, responsible for fatty acid synthesis.

Due to the both activities, shoot and rhizome growth comes to an end and shoots

meristems and rhizome buds begin to die.

Auxin Mimics [62,66]

Some herbicides are referred as synthetic auxins. Auxins are plant hormones

that regulate growth processes in many plant cell/tissues. If susceptible plants are

treated with these herbicides, they show symptoms that possibly called „auxin

overdose‟ and finally die due to the uncontrolled and disorganized growth.

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 21

1.5 Heterocyclic Compounds as Plant Growth Regulators

Common name : Indole acetic acid (IAA) CH2COOH

Class : Auxin
Chemical class : Indole
Function : Stimulates cell elongation N
H

Common name : Indole butyric acid (IBA) CH2CH2CH2COOH

Class : Auxin
Chemical class : Indole
Function : Stimulates cell elongation N
H

Common name : Zeatin

OH
Class : Cytokinin HN

Chemical class : Purine N

N
Function : Stimulates cell division
N N
H

NH2
Common name : Adenine
Class : Cytokinin N
N

Chemical class : Purine

N
Function : Stimulates cell division N H

Common name : 6-Benzylaminopurine (6-BAP) HN Ph

Class : Cytokinin N
N
Chemical class : Purine
N
Function : Stimulates cell division N H

Common name : Kinetin

HN
Class : Cytokinin O
N
Chemical class : Purine N

Function : Stimulates cell division N N

H

O
Common name : Gibberellic acid
OC OH
Class : Gibberellins HO
Chemical class : Gibberellin CH2
Function : Stem cell elongation H3C
COOH

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 22

Common name : Ancymidol OH

Class : Growth inhibitor
Chemical class : Pyrimidine
N
Function : Inhibition of gibberellin OCH3
N
biosynthesis

Common name : Dikegulac COOH

O
Class : Growth inhibitor O
O
Chemical class : Cyclohexaketone
O O
Function : Inhibition of amino acid up
take by cell

Common name : Isopyrimol

OH
Class : Growth inhibitor
Chemical class : Pyrimidine
Function : Inhibition of gibberellin N
Cl
biosynthesis N

Common name : Maleic hydrazide

Class : Growth inhibitor
O O
Chemical class : Hydrazide
Function : Inhibits cell division HN NH

Common name : Mepiquat chloride H3C Cl CH3

Class : Growth inhibitor N
Chemical class : Piperidine
Function : Disturbs gibberellin
biosynthesis

Common name : Tiaojiean H3C Cl CH3

Class : Growth inhibitor N
Chemical class : Morpholine
Function : Disturbs biosynthetic O
processes

Common name : Piproctanyl bromide 3,7-methyloctyl

Br
Class : Growth inhibitor N
Chemical class : Piperidine
Function : Disturbs biosynthetic processes

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 23

Common name : Dimethipin

Class : Desiccant O O
Chemical class : Dithiin S S
O
Function : Disturbs protein synthesis O

Common name : Endothall COOH

Class : Desiccant O
Chemical class : Carboxylic acid
COOH
Function : Inhibits respiration &
interferes with protein synthesis

Common name : Paraquat dichloride

Class : Desiccant H3C N N CH3

Chemical class : Bipyridine Cl Cl

Function : Damage of plant cells by
interference in electron
transfer system

Common name : Thidiazuron O

Class : Defoliant /desiccant, N

N N
Cytokinin-like N H H
S
Chemical class : Urea
Function : Interfers in photosynthesis,
callus induction

Common name : Flurprimidol OH

Class : Growth retardant
Chemical class : Pyrimidine
N
Function : Inhibits gibberellin OCF3
N
biosynthesis

N
Common name : Paclobutrazol
N Cl
Class : Growth retardant N

Chemical class : Triazole

Function : Antagonist for gibberellin OH

N
Common name : Tetcyclacis N

Class : Growth retardant N

Chemical class : Triazole

N
Function : Antagonist for gibberellin N Cl

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 24
N
Common name : Uniconazole
N Cl
Class : Growth retardant N

Chemical class : Triazole

Function : Antagonist for gibberellin OH

Cl
Common name : Inabenfide
N
Class : Growth retardant
Chemical class : Anilide
Function : Inhibits gibberellin NH
biosynthesis O HO

Common name : Forchlorfenuron Cl O

Class : Growth stimulator
Chemical class : Urea N N N
H H
Function : Enhance cell division

Common name : Hymexazol O N

Class : Growth stimulator
Chemical class : Oxazole H3C OH
Function : Promots rooting

1.6 Heterocyclic Compounds as Herbicides

Common name : Tebuthiuron O

N N
Class : Nonselective CH3
Chemical class : Urea HN N
S CH3
Function : Inhibits photosynthesis, CH3 CH3 CH3
RNA and lipid syntheses

Common name : Methabenzthiazuron O

N
Class : Selective
Chemical class : Urea N N CH3
H
Function : Inhibition of photosynthetic S CH3
electron transport (PS II)

Common name : Amitrol

N
Class : Nonselective HN
Chemical class : Triazole NH2
Function : Prevents chlorophyll N
development

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 25

Common name : Isouron CH3

H3C
O
Class : Selective H3C
Chemical class : Urea N N CH3
Function : Inhibits the Hill reaction in O H
N CH3
chloroplast

Common name : Imazethapyr O H

N N
Class : Selective C2H5
Chemical class : Imidazole H3C N
Function : Disrupts in protein CH3
HOOC
CH3
synthesis

Common name : Buthidazole O N N

CH3
Class : Selective H3C
N
N
Chemical class : Imidazole/thidazole S CH3
CH3
Function : Inhibits RNA and lipid
OH
syntheses

Common name : Thiazafluron N N O

Class : Nonselective F3C CH3
Chemical class : Urea S N N
Function : Inhibits photosynthesis H
CH3

Common name : Aminopyralid NH2

Class : Selective Cl
Chemical class : Pyrimidine
Function : Stop cell division, Cl N COOH
also auxin like

Common name : Picloram NH2

Class : Selective Cl Cl
Chemical class : Pyrimidine
Function : Stop cell division,
Cl N COOH
also auxin like

Common name : Halauxifen-methyl H3CO F NH2

Class : Selective
Cl Cl
Chemical class : Pyrimidine
Function : Necrosis & malformation N

of leaf COOCH3

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 26

Common name : Benazolin-ethyl COOC2H5

Class : Selective N

Chemical class : Benzothiazolone O

Function : Affects protein synthesis S

Cl

Common name : Fenthiaprop-ethyl

N COOC2H5
Class : Selective
O O
Chemical class : Benzothiazole
S CH3
Function : Inhibits fatty acid Cl

biosynthesis

Common name : Mefenacet O

N
Class : Selective O
Chemical class : Anilide/benzothiazole S
N
Function : Inhibits VLCFAs CH3

Common name : Azimsulfuron H3CO H3C

O
N O N
Class : Selective N
Chemical class : Sulfonylurea N N S
H H
Function : Inhibits biosynthesis of N O
the essential amino acids H3CO
N
N
N
N

CH3
Common name : Difenzoquat H3C CH3
N N CH3SO4
Class : Selective
Chemical class : Pyrazole
Function : Causes chlorosis & necrosis
in leaves

Common name : Halosulfuron-methyl H3CO H3C

O
N O
Class : Selective N
N
Chemical class : Sulfonylurea N
H
N
H
S
Function : Inhibits ALS & AHAS N O Cl
H3CO H3COOC

O
Common name : Metazachlor N
Cl
N
Class : Selective N

Chemical class : Acetanilide H3C CH3

Function : Inhibits VLCFAs (KCS)

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 27
CHF2
Common name : Pyroxasulfone CH3
H3C O O
Class : Selective N N
H3C O
Chemical class : Pyrazole N
S
Function : VLCFAEs inhibitor
O
CF3

Cl

Common name : Atrazine

N N
Class : selective
Chemical class : Triazine C2H5 CH(CH3)2
N N N
Function : Photosynthesis (PS II) H H
Inhibitor (binds to protein)

Common name : Flucarbazone F3CO

Class : selective O H
N
Chemical class : Triazolone/sulfonylurea S
Function : Inhibits ALS & AHAS O N O O
N
N
H3C
OCH3

1.7 Statement of the Present Work

The present research work on the synthesis and studies on PGR activities,

involves designing of heterocyclic compounds, containing N, S atoms as well as

bioactive functional groups and investigation of PGR activities. The reactions are

carried out by facile synthetic procedures. Procedures are also developed in terms of

mild reaction conditions, ease of work up, use of readily available and economical

reagents, solvents, catalysts and minimum use of source of external energy.

Encouraging PGR activities of heterocyclic compounds have indicated their

possibility for further discovery as excellent plant growth regulators and/or herbicides

leading to the prosperity of agriculture. For this reason, we have synthesized and

critically characterized three series of heterocyclic compounds by utilizing

sophisticated spectroscopic tools. In addition, we have investigated their plant growth

regulator activities on crops i.e. wheat, mung bean and in plant tissue culture assay on

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 28

medicinally important plant i.e. Glacirrhiza glabra. Further they were also subjected

to antimicrobial assay against fungal and bacterial species. The discussion regarding

synthesis, characterization and activities has been discussed in the next chapters.

References

[1] S. B. Salunke, Md. Qudrathullah, C. M. Bhavsar and B. B. Deogadkar,

“Physical and Agrochemistry” (2nd Edition), 1988, Nirali Prakashan, Pune.

[2] L. G. Nickell, “Plant Growth Substances”, 1979, American Chemical Society.

[3] G. S. Avery, Ohio Journal of Science, 1937, 37 (6), 317-332.

[4] F. M. Fishel, Institute of Food and Agricultural Sciences, University of Florida,

2006, Document No. PI-102 (http://edis.ifas.ufl.edu).

[5] R. N. Arteca, “Plant Growth Substances: Principles and Applications”, 1996,

New York: Chapman & Hall.

[6] P. J. Davies, “Plant Hormones: Physiology, Biochemistry and Molecular

Biology”, 1995, Dordrecht: Kluwer.

[7] C. Darwin, “The power of movement in plants”, 1880, London: John Murray.

[8] E. Salkowski, Zeitschr. Physiol. Chem., 1885, 9, 23-33.

[9] F. W. Went, Proceedings of the Koninklijke Nederlandse Akademie van

Wetenschappen, 1926, 30, 10-19.

[10] F. W. Went, Rec. Trav. Bot. Neerland., 1928, 24, 1-116.

[11] F. Kogl, and A. J. Haagen-Smit, Proc. Sect. Sci., 1931, 34, 1411-1416.

[12] B. Bartel, Annu. Rev. Plant Physiology and Plant Molecular Biology, 1997, 48,

51-66.

[13] L. Taiz and E. Zeiger, “Plant Physiology” (5 th Edition), online book.

[14] www.planthormones.info/auxins.htm

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 29

[15] R. L. Jones and D. J. Phillips, Plant Physiology, 1966, 41, 1381-1386.

[16] E. Kurosawa, Natural History Society of Formosa, 1926, 16, 213-227.

[17] T. Yabuta, Nogyo-oyobi-Engei, 1935, 10, 17.

[18] T. Yabuta and Y. Sumiki, Journal of the Agricultural Chemical Society of

Japan, 1938, 14, 1526.

[19] H. Kato, Life Science: Structural Biology, Research Frontiers, 2009.

[20] A. Boga, S. Binokay and Y. Sertdemir, Turkish Journal of Biology, 2009, 33,

181-188.

[21] Z. -H. Liu, W. -S. Chen and C. -H. Chou, “Roles of Plant Growth Regulating

Substances”, Encyclopedia of Life Support Systems (EOLSS), Physiology and

Mentainance-V.

[22] P. Hedden and Y. Kamiya, Annu. Rev. Plant Physiology and Plant Molecular

Biology, 1997, 48, 431-460.

[23] www.planthormones.info/gibberellins.htm

[24] J. J. Kieber and G. E. Schaller, Plant Physiology, 2010, 154, 487-492.

[25] J. Van Overbeek, M. E. Conklin and A. F. Blakeslee, Science, 1941, 94, 350-

351.

[26] C. O. Miller, F. Skoog, M. H. Von Saltza and F. M. Strong, Journal of the

American Chemical Society, 1955, 77, 1392.

[27] C. O. Miller, F. Skoog, F. S. Okumura, M. H. von Saltza and F. M. Strong,

Journal of the American Chemical Society, 1956, 78, 1375-1380.

[28] F. Skoog and C. O. Miller, Symposia of the Society for Experimental Biology,

1957, 11, 118-131.

[29] D. S. Letham, Life Sciences, 1963, 2 (8), 569-573.

[30] G. A. Romanov, Russian Journal of Plant Physiology, 2009, 56 (2), 268-290.

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 30

[31] G. Haberer and J. J. Kieber, Plant Physiology, 2002, 128, 354-362.

[32] E. F. George, A. Michael Hall and G. -J. DeKlerk, “Plant Propagation by Tissue

Culture” (3rd Edition), 2008, Springer.

[33] www.planthormones.info/ cytokinins.htm

[34] K. R. Stern, Bidlak and Janskey, “Introductory Plant Biology” (11 th Edition),

2008.

[35] S. L. Doubt, Botanical Gazette, 1917, 63, 209-224.

[36] R. P. Wintz, Thesis (Effects on Carnation Cut Flowers of Storage with Grocery

Produce), 1956, 13.

[37] R. Gane, Nature, 1934, 134, 1008.

[38] W. Crocker, A. E. Hitchcock and P. W. Zimmerman, Contributions from Boyce

Thompson Institute, 1935, 7, 231-248.

[39] S. P. Burg and K. V. Thimann, Proceedings of the National Academy of

Sciences, 1959, 45 (3), 335-344.

[40] A. B. Bleecker and H. Kende, Annual Review of Cell and Developmental

Biology, 2000, 16, 1-18.

[41] L. Taiz and E. Zeiger, “Plant Physiology” (5th Edition), online book.

[42] www.planthormones.info/ ethylene.htm

[43] M. K. Jensen, S. Lindemose, F. de Masi, J. J. Reimer, M.l Nielsen, V. Perera, C.

T. Workman, F. Turck, M. R. Grant, J. Mundy, M. Petersen and K. Skriver,

Federation of European Biochemical Societies Open Bio, 2013, 3, 321-327.

[44] F. T. Addicott, H. R. Carns, J. L. Lyon, O. E. Smith and J. L. McMeans, J. P.

Nitsch, (Ed.), “On the physiology of abscission”, Paris: Cent. Nat. Rech. Sci.,

1964, 687-703.

[45] F. T. Addicott and J. L. Lyon, Annu. Rev. Plant Physiology, 1969, 20, 139-64

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 31

[46] S. N. Pandey and B. K. Sinha, “Plant Physiology” (4 th Edition), 2008, Vikas

Publising House Pvt Ltd.

[47] A. J. Cutler and J. E. Krochko, Trends in Plant Science, 1999, 4 (12), 472-477.

[48] www.plant-hormones.info/abscisicacid.htm

[49] Germination: Launching the Seed, WFP062298, 1998, Wisconsin Fast Plants.

[50] G. Blythe and J. L. Sibley, Combined Proceedings International Plant

Propagators’ Society, 2003, 53, 406-410.

[51] T. Gaspar, C. Kevers, C. Penel, H. Greppin, D. M. Reid and T. A. Thorpe, In

Vitro Cellular & Developmental Biology - Plant, 1996, 32 (4), 272-289.

[52] S. Rao, P. Patil, C. P. Kaviraj, Indian Journal of Biotechnology, 2005, 4, 556-

560.

[53] The Scoop on Horticulture, Austin Outdoor, 2010, 1-3.

[54] J. G. Latime and H. Scoggins, Virginia Cooperative Extension, Publication 430-

103, 2012, 1-40.

[55] C. G. Forshey, New York’s Food and Life Sciences bulletin, 1986, 116, 1-7.

[56] J. C. Sellmer, V. J. Cotrone, M. R. McGann and J. R. Nuss, “Pruning

Ornamental Plants”, 2004, Agricultural Research and Cooperative Extension.

[57] G. F. Ryan, Journal of Environmental Horticulture, 1985, 3 (1), 15-18.

[58] F. M. Fishel, Institute of Food and Agricultural Sciences, University of Florida,

2006, Document No. PI-101 (http://edis.ifas.ufl.edu).

[59] S. T. Ball and C. Glover, Cooperative Extension Service, Guide A-217, 1999, 1-

8.

[60] S. Singal, M. Kumud and S. Thakral, Indian Journal of Natural Product and

Resources, 2012, 3 (1), 61-64.

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.
CHAPTER 1 32

[61] U. S. Sree Ramulu, “Chemistry of Herbicides” (2nd Edition), 1985, Mohan

Primalani for Oxford & IBH Publishing Co., New Delhi.

[62] M. Tu, C. Hurd and J. M. Randall, "Weed Control Methods Handbook: Tools &

Techniques for Use in Natural Areas" The Nature Conservancy, 2001.

[63] S. O. Duke, P. C. Kearny (Ed.) and D. D. Kaufman (Ed.), “Glyphosate in

Herbicides: Chemistry, Degradation, and Mode of Action”, 1988, Marcel

Dekker, Inc. New York, New York.

[64] C. L. Cespedes, J. S. Caldero, B. K. Diaz, and B. L. Hennsen, Journal of

Agricultural and Food Chemistry, 1998, 46 (7), 2810-2816.

[65] D. Peterson, C. R. Thompson, D. E. Shoup, B. L. Olson, “Herbicide Mode of

Action”, 2013, Kansas State University Agricultural Experiment Station and

Cooperative Extension.

[66] K. Grossmann, Plant Signaling & Behavior, 2007, 2 (5), 421-423.

Ph. D. Thesis, Mr. Dipesh P. Mahajan, School of Chemical Sciences, NMU, Jalgaon.