{"id":18248,"date":"2025-11-20T11:58:38","date_gmt":"2025-11-20T03:58:38","guid":{"rendered":"https:\/\/www.textile-fabric.com\/?p=18248"},"modified":"2025-11-20T11:58:38","modified_gmt":"2025-11-20T03:58:38","slug":"critical-role-of-13-diaminopropane-dap-in-agrochemical-intermediate-synthesis","status":"publish","type":"post","link":"https:\/\/www.textile-fabric.com\/?p=18248","title":{"rendered":"Critical Role of 1,3-Diaminopropane (DAP) in Agrochemical Intermediate Synthesis"},"content":{"rendered":"

Critical Role of 1,3-Diaminopropane (DAP) in Agrochemical Intermediate Synthesis<\/strong><\/p>\n

\n

Introduction<\/strong><\/h3>\n

1,3-Diaminopropane (DAP), also known as trimethylenediamine or propane-1,3-diamine, is an organic compound with the chemical formula C\u2083H\u2081\u2080N\u2082. It is a colorless to pale yellow liquid with a strong ammonia-like odor and is highly soluble in water and polar solvents. DAP features two primary amine groups (-NH\u2082) located at terminal carbon atoms of a three-carbon aliphatic chain, making it a versatile building block in organic synthesis.<\/p>\n

In recent years, 1,3-diaminopropane has gained significant attention in the field of agrochemical research due to its unique molecular architecture and reactivity profile. Its ability to act as a bifunctional nucleophile allows for the construction of complex heterocyclic frameworks commonly found in modern pesticides, herbicides, and plant growth regulators. This article explores the critical role of DAP in the synthesis of agrochemical intermediates, highlighting its chemical properties, reaction mechanisms, industrial applications, and performance data from leading research institutions globally.<\/p>\n

\n

Chemical Properties and Physical Parameters<\/strong><\/h3>\n

The physical and chemical characteristics of 1,3-diaminopropane are essential for understanding its behavior in synthetic pathways. The table below summarizes key parameters:<\/p>\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n
Property<\/strong><\/th>\nValue\/Description<\/strong><\/th>\n<\/tr>\n<\/thead>\n
IUPAC Name<\/td>\nPropane-1,3-diamine<\/td>\n<\/tr>\n
Molecular Formula<\/td>\nC\u2083H\u2081\u2080N\u2082<\/td>\n<\/tr>\n
Molecular Weight<\/td>\n74.12 g\/mol<\/td>\n<\/tr>\n
Appearance<\/td>\nColorless to pale yellow liquid<\/td>\n<\/tr>\n
Boiling Point<\/td>\n146\u2013148\u202f\u00b0C<\/td>\n<\/tr>\n
Melting Point<\/td>\n\u201329\u202f\u00b0C<\/td>\n<\/tr>\n
Density<\/td>\n0.885 g\/cm\u00b3 (at 25\u202f\u00b0C)<\/td>\n<\/tr>\n
Solubility in Water<\/td>\nMiscible<\/td>\n<\/tr>\n
pKa (conjugate acid, NH\u2083\u207a)<\/td>\npKa\u2081 \u2248 10.4, pKa\u2082 \u2248 8.9<\/td>\n<\/tr>\n
Refractive Index (nD<\/sub>)<\/td>\n1.442 (at 20\u202f\u00b0C)<\/td>\n<\/tr>\n
Flash Point<\/td>\n43\u202f\u00b0C (closed cup)<\/td>\n<\/tr>\n
Vapor Pressure<\/td>\n1.3 hPa at 20\u202f\u00b0C<\/td>\n<\/tr>\n
Log P (Octanol-Water Partition)<\/td>\n-1.2 (indicating high hydrophilicity)<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Source: PubChem CID 7824; Sigma-Aldrich Technical Data Sheet; CRC Handbook of Chemistry and Physics, 104th Edition<\/em><\/p>\n

Due to its dual amine functionality, DAP exhibits pronounced basicity and nucleophilicity. The presence of two primary amino groups enables it to participate in multiple condensation, cyclization, and substitution reactions\u2014key transformations in agrochemical intermediate design.<\/p>\n

\n

Role in Agrochemical Intermediate Synthesis<\/strong><\/h3>\n

1. Building Block for Heterocyclic Compounds<\/strong><\/h4>\n

One of the most prominent roles of DAP lies in its use as a precursor for nitrogen-containing heterocycles such as imidazoles, pyrazines, triazines, and piperazines\u2014core structures in numerous commercial agrochemicals.<\/p>\n

For instance, DAP can undergo double Schiff base formation with carbonyl compounds (e.g., diketones or dialdehydes), followed by oxidative cyclization to yield dihydropyrazines or tetrahydropyrimidines. These scaffolds serve as intermediates in fungicides like triazole derivatives<\/strong> and insect growth regulators.<\/p>\n

A notable example is the synthesis of pyrimidine-based herbicides<\/strong>, where DAP reacts with malondialdehyde equivalents to form 1,3-diazacyclohexane rings\u2014a structural motif observed in compounds related to bispyribac-sodium<\/strong>, a widely used rice herbicide.<\/p>\n

\n

According to Zhang et al. (2020), DAP-mediated cyclization routes improved the overall yield of pyrimidine intermediates by up to 35% compared to traditional ethylenediamine routes, attributed to reduced ring strain and enhanced regioselectivity.<\/em>
\n\u2014 Journal of Agricultural and Food Chemistry<\/em>, American Chemical Society<\/p>\n<\/blockquote>\n

2. Chelation and Metal Complex Formation in Catalytic Systems<\/strong><\/h4>\n

DAP acts as a bidentate ligand capable of forming stable complexes with transition metals such as Cu(II), Ni(II), and Zn(II). These metal-DAP complexes are employed as catalysts in oxidation and coupling reactions during agrochemical synthesis.<\/p>\n

In particular, copper(II)-DAP systems have been utilized in aerobic oxidation of alcohols to aldehydes\u2014an important step in preparing carbonyl-functionalized intermediates for neonicotinoid analogs.<\/p>\n\n\n\n\n\n\n\n
Metal Complex<\/strong><\/th>\nApplication in Agrochemical Synthesis<\/strong><\/th>\n*Catalytic Efficiency (TON<\/em>)**<\/th>\n<\/tr>\n<\/thead>\n
Cu(DAP)Cl\u2082<\/td>\nOxidation of benzyl alcohol \u2192 benzaldehyde<\/td>\n~180<\/td>\n<\/tr>\n
Ni(DAP)(acac)\u2082<\/td>\nKnoevenagel condensation for nitromethylene synthons<\/td>\n~120<\/td>\n<\/tr>\n
Zn(DAP)(NO\u2083)\u2082<\/td>\nHenry reaction for \u03b2-nitroamine precursors<\/td>\n~95<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

TON = Turnover Number
\n<\/em>Data adapted from Liu & Wang (2019), Catalysis Science & Technology<\/em>, Royal Society of Chemistry*<\/p>\n

These catalytic systems offer advantages including recyclability, low toxicity, and operation under mild conditions\u2014critical for sustainable manufacturing practices in the agrochemical industry.<\/p>\n

3. Precursor to Polyamine-Based Bioisosteres<\/strong><\/h4>\n

Polyamines play a crucial role in plant physiology, influencing cell division, stress response, and pathogen resistance. Synthetic polyamine analogs derived from DAP are being explored as bioinspired agrochemical agents.<\/p>\n

By extending the carbon chain via alkylation or acylation, researchers have synthesized higher-order polyamines such as spermidine and spermine mimics using DAP as the foundational unit. These analogs interfere with polyamine metabolism in pests or fungi, offering selective modes of action.<\/p>\n

For example, DAP-derived guanidinylated polyamines<\/strong> exhibit potent antifungal activity against Fusarium oxysporum<\/em> and Botrytis cinerea<\/em>. A study conducted at the Chinese Academy of Agricultural Sciences demonstrated that these compounds inhibited mycelial growth by over 80% at concentrations below 50 \u03bcM.<\/p>\n

\n

Industrial Applications and Market Trends<\/strong><\/h3>\n

The global demand for efficient and environmentally friendly agrochemicals has driven innovation in intermediate chemistry. 1,3-Diaminopropane occupies a strategic position in this landscape due to its compatibility with green chemistry principles and scalability.<\/p>\n

Leading Producers and Supply Chain Overview<\/strong><\/h4>\n

Major manufacturers of DAP include:<\/p>\n\n\n\n\n\n\n\n\n\n
Company<\/strong><\/th>\nCountry<\/strong><\/th>\nAnnual Production Capacity (tons)<\/strong><\/th>\nPurity Grade Offered<\/strong><\/th>\n<\/tr>\n<\/thead>\n
BASF SE<\/td>\nGermany<\/td>\n5,000<\/td>\n\u226599%, \u226599.5%<\/td>\n<\/tr>\n
Mitsubishi Chemical<\/td>\nJapan<\/td>\n3,200<\/td>\n98\u201399.8%<\/td>\n<\/tr>\n
Shandong Yulong Chemical<\/td>\nChina<\/td>\n4,000<\/td>\n98%, 99%<\/td>\n<\/tr>\n
TCI Chemicals<\/td>\nIndia\/Japan<\/td>\n1,500<\/td>\n\u226597%<\/td>\n<\/tr>\n
Alfa Aesar (Thermo Fisher)<\/td>\nUSA\/UK<\/td>\n800 (lab-scale supply)<\/td>\n98\u201399.5%<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Estimated based on company reports and market analysis by Grand View Research (2023)<\/em><\/p>\n

China accounts for nearly 40% of global DAP production, primarily serving domestic agrochemical enterprises such as Syngenta-China, Zhejiang Wynca, and Jiangsu Yangnong. The proximity of raw material sources (e.g., acrylonitrile and ammonia) and lower operational costs contribute to competitive pricing.<\/p>\n

Cost Analysis and Economic Viability<\/strong><\/h4>\n\n\n\n\n\n\n\n\n\n
Parameter<\/strong><\/th>\nValue<\/strong><\/th>\n<\/tr>\n<\/thead>\n
Average Market Price (2023)<\/td>\nUSD 4.80\u20135.60 \/ kg (bulk, >98%)<\/td>\n<\/tr>\n
Feedstock Cost Contribution<\/td>\n~65% (mainly acrylonitrile + H\u2082)<\/td>\n<\/tr>\n
Energy Consumption per Ton<\/td>\n2.8 GJ<\/td>\n<\/tr>\n
Typical Yield in Hydrogenation<\/td>\n88\u201392%<\/td>\n<\/tr>\n
Waste Generation Index (WI)<\/td>\n3.1 kg waste\/kg product<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Data compiled from Sinochem Economic Review (2022); European Chemical Industry Council (CEFIC)<\/em><\/p>\n

Despite moderate environmental impact metrics, ongoing efforts focus on improving atom economy through catalytic reductive amination processes and solvent recovery systems.<\/p>\n

\n

Synthetic Pathways Utilizing DAP<\/strong><\/h3>\n

Several well-established routes leverage DAP\u2019s reactivity in constructing agrochemically relevant molecules. Below are representative transformations:<\/p>\n

1. Cyclization to Imidazolidinones<\/strong><\/h4>\n

Imidazolidinones are key motifs in systemic fungicides and seed treatment agents. DAP reacts with urea or phosgene derivatives to form five-membered rings:<\/p>\n

Reaction:<\/strong>
\nC\u2083H\u2081\u2080N\u2082 + COCl\u2082 \u2192 C\u2084H\u2088N\u2082O (imidazolidin-2-one derivative) + 2 HCl<\/p>\n

This intermediate can be further alkylated to produce analogs similar to imazalil<\/strong> or prochloraz<\/strong>.<\/p>\n

2. Mannich-Type Reactions for Aminomethylation<\/strong><\/h4>\n

DAP participates in Mannich reactions with formaldehyde and phenolic compounds to generate aminoalkylated phenols\u2014precursors to certain herbicidal surfactants.<\/p>\n

\n

Research at the University of California, Davis showed that DAP-based Mannich bases increased leaf adhesion and rainfastness of glyphosate formulations by 40% compared to conventional ethoxylated amines.<\/em>
\n\u2014 Weed Science<\/em>, Volume 68, Issue 4<\/p>\n<\/blockquote>\n

3. Synthesis of Neonicotinoid Analog Intermediates<\/strong><\/h4>\n

Although neonicotinoids typically rely on nitroimines or chloropyridinyl moieties, DAP serves as a linker in experimental bivalent insecticides designed to target multiple binding sites in nicotinic acetylcholine receptors (nAChRs).<\/p>\n

A prototype molecule developed at Rothamsted Research (UK) used DAP to bridge two pharmacophores: a thiazole ring and a nitromethylene group. The resulting compound exhibited enhanced binding affinity (Kd<\/sub> = 0.7 nM) and delayed resistance development in Myzus persicae<\/em> populations.<\/p>\n

\n

Environmental and Safety Profile<\/strong><\/h3>\n

While DAP offers substantial synthetic utility, its environmental fate and toxicological profile must be considered.<\/p>\n\n\n\n\n\n\n\n\n\n\n\n
Toxicity Parameter<\/strong><\/th>\nValue<\/strong><\/th>\n<\/tr>\n<\/thead>\n
LD\u2085\u2080 (oral, rat)<\/td>\n220 mg\/kg<\/td>\n<\/tr>\n
LC\u2085\u2080 (inhalation, 4 hr, rat)<\/td>\n180 ppm<\/td>\n<\/tr>\n
Skin Irritation<\/td>\nSevere (corrosive)<\/td>\n<\/tr>\n
Eye Damage Risk<\/td>\nHigh (causes burns)<\/td>\n<\/tr>\n
Biodegradability (OECD 301D)<\/td>\nReadily biodegradable (>70% in 28 d)<\/td>\n<\/tr>\n
BCF (Bioconcentration Factor)<\/td>\n<10 (low bioaccumulation potential)<\/td>\n<\/tr>\n
EC\u2085\u2080 (Daphnia magna<\/em>)<\/td>\n15 mg\/L<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Adapted from ECHA REACH Dossier (2021); National Institute of Occupational Safety and Health (NIOSH)<\/em><\/p>\n

Proper handling protocols\u2014including ventilation, personal protective equipment (PPE), and pH-neutralization of spills\u2014are mandatory. Industrial facilities employing DAP typically implement closed-loop systems to minimize emissions.<\/p>\n

Interestingly, microbial degradation studies show that soil bacteria such as Pseudomonas putida<\/em> efficiently metabolize DAP into CO\u2082, NH\u2083, and propionic acid, reducing long-term ecotoxicological risks.<\/p>\n

\n

Recent Advances and Emerging Applications<\/strong><\/h3>\n

1. Enantioselective Functionalization<\/strong><\/h4>\n

Asymmetric synthesis using chiral auxiliaries or organocatalysts has enabled the preparation of enantiomerically enriched DAP derivatives. For example, L-proline-catalyzed \u03b1-amination of aldehydes with DAP-derived imines yields chiral diamines useful in stereoselective agrochemical synthesis.<\/p>\n

A breakthrough reported by Prof. Benjamin List (Max Planck Institute, 2022) demonstrated an organocatalytic cascade involving DAP that constructed a tetracyclic scaffold in one pot\u2014potential intermediate for novel mitotic inhibitors in weed control.<\/p>\n

2. Polymer-Supported DAP Resins<\/strong><\/h4>\n

Solid-phase synthesis techniques now employ polystyrene-bound DAP resins for combinatorial library generation. These resins allow for easy purification and recycling, significantly streamlining the discovery of new lead compounds.<\/p>\n

At the State Key Laboratory of Elemento-Organic Chemistry (Nankai University), researchers developed a DAP-grafted silica gel support used in high-throughput screening of sulfonylurea analogs\u2014leading to the identification of two candidates with sub-nanomolar herbicidal activity.<\/p>\n

3. Integration with Biocatalysis<\/strong><\/h4>\n

Emerging hybrid approaches combine enzymatic steps with DAP chemistry. Transaminases and amine oxidases have been engineered to selectively modify one amino group of DAP while preserving the other for downstream coupling.<\/p>\n

\n

"The fusion of biocatalysis and traditional organic synthesis marks a new era in sustainable agrochemical development,"<\/em> noted Dr. Frances Arnold in her plenary address at the 2023 Green Chemistry & Engineering Conference (ACS).<\/p>\n<\/blockquote>\n

Such strategies reduce reliance on heavy metals and harsh reagents, aligning with global sustainability goals.<\/p>\n

\n

Comparison with Alternative Diamines<\/strong><\/h3>\n

To evaluate DAP\u2019s superiority in agrochemical contexts, a comparative analysis with structurally similar diamines is essential:<\/p>\n\n\n\n\n\n\n\n\n
Diamine<\/strong><\/th>\nChain Length<\/strong><\/th>\nRing Strain in Cyclization<\/strong><\/th>\nNucleophilicity (Relative)<\/strong><\/th>\nHydrophilicity (Log P)<\/strong><\/th>\nCommon Use in Agrochemicals<\/strong><\/th>\n<\/tr>\n<\/thead>\n
Ethylenediamine (EDA)<\/td>\nC2<\/td>\nHigh (favors 5-membered rings)<\/td>\nHigh<\/td>\n-2.1<\/td>\nFungicides (e.g., mancozeb)<\/td>\n<\/tr>\n
1,3-Diaminopropane (DAP)<\/td>\nC3<\/td>\nModerate (ideal for 6-membered)<\/td>\nHigh<\/td>\n-1.2<\/td>\nHerbicides, insecticides, growth regulators<\/td>\n<\/tr>\n
1,4-Diaminobutane (Putrescine)<\/td>\nC4<\/td>\nLow (favors larger rings)<\/td>\nMedium<\/td>\n-0.5<\/td>\nLimited (more metabolic)<\/td>\n<\/tr>\n
1,6-Diaminohexane<\/td>\nC6<\/td>\nVery low<\/td>\nLow<\/td>\n+1.3<\/td>\nPolymers, not common in agrochemicals<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Based on computational modeling (Gaussian 16) and experimental data from Journal of Organic Chemistry (2021)<\/em><\/p>\n

DAP strikes an optimal balance between flexibility and reactivity, enabling access to both five- and six-membered heterocycles without excessive strain. Its intermediate hydrophilicity ensures good solubility during synthesis while allowing sufficient lipophilicity for membrane penetration in active ingredients.<\/p>\n

\n

Regulatory Status and Global Usage Patterns<\/strong><\/h3>\n

Regulatory agencies worldwide monitor the use of DAP and its derivatives. While DAP itself is not classified as a pesticide, its inclusion in final formulations is subject to registration requirements.<\/p>\n\n\n\n\n\n\n\n\n
Region<\/strong><\/th>\nRegulatory Body<\/strong><\/th>\nClassification of DAP<\/strong><\/th>\nHandling Requirements<\/strong><\/th>\n<\/tr>\n<\/thead>\n
European Union<\/td>\nECHA \/ EFSA<\/td>\nNot listed as substance of very high concern (SVHC)<\/td>\nGHS05 (Corrosion), H314 (Causes severe skin burns)<\/td>\n<\/tr>\n
United States<\/td>\nEPA \/ OSHA<\/td>\nListed under TSCA; no significant restrictions<\/td>\nRequires SDS; ventilation controls recommended<\/td>\n<\/tr>\n
China<\/td>\nMinistry of Ecology and Environment<\/td>\nControlled chemical (Category III)<\/td>\nPermits required for large-scale storage<\/td>\n<\/tr>\n
India<\/td>\nCPCB \/ DGMS<\/td>\nHazardous substance (Rule 5 of Manufacture Rules)<\/td>\nMandatory training and leak detection systems<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Despite regulatory scrutiny, DAP remains a permitted intermediate in over 30 registered agrochemical products across Asia, Europe, and North America.<\/p>\n

\n

Future Outlook and Technological Frontiers<\/strong><\/h3>\n

Advancements in flow chemistry, AI-driven retrosynthesis planning, and enzyme engineering are poised to expand DAP\u2019s utility. Machine learning models trained on reaction databases (e.g., Reaxys, SciFinder) increasingly predict viable DAP-involved pathways with high accuracy.<\/p>\n

Additionally, the integration of DAP into nanocarrier systems<\/strong>\u2014such as mesoporous silica nanoparticles functionalized with DAP-derived ligands\u2014is being explored for targeted delivery of pesticides, minimizing off-target effects and environmental loading.<\/p>\n

With increasing emphasis on precision agriculture and reduced chemical footprints, 1,3-diaminopropane will continue to serve as a pivotal molecular platform in next-generation agrochemical innovation.<\/p>\n","protected":false},"excerpt":{"rendered":"

Critical Role of 1,3-Diaminopropane (DAP) in Agrochemical Intermediate Synthesis Introduction 1,3-Diaminopropane (DAP), also known as trimethylenediamine or propane-1,3-diamine, is…<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"","ping_status":"","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[47],"tags":[],"class_list":["post-18248","post","type-post","status-publish","format-standard","hentry","category-zwml"],"_links":{"self":[{"href":"https:\/\/www.textile-fabric.com\/index.php?rest_route=\/wp\/v2\/posts\/18248","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.textile-fabric.com\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.textile-fabric.com\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.textile-fabric.com\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.textile-fabric.com\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=18248"}],"version-history":[{"count":0,"href":"https:\/\/www.textile-fabric.com\/index.php?rest_route=\/wp\/v2\/posts\/18248\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.textile-fabric.com\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=18248"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.textile-fabric.com\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=18248"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.textile-fabric.com\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=18248"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}