(I am using the normally accepted equation ignoring the fact that the Mg(OH)Br will react further with the acid.). This is the third video in the sequence: Part 1 (preparation for the reaction). The two wires shown in the figure carry currents of I = 5.37 A in opposite directions and are separated by a distance of d 0 = 8.78 cm. So I'm hoping you all can figure out what's missing. A greener approach to a traditional Grignard Reaction has been implemented by Dr. Abby OConnor at the College of New Jersey (TCNJ). Synthesis of Arylglycines by Reaction of Diethyl N-Boc-iminomalonate with
The greener approach reduces the use of undesirable ethers, and avoids the use of hexanes, and magnesium. [*~1D5)`0ZZ28@P(5^ P[X#[h-uYXTs2[ xrAMj)*?GEUwcombJ"TMJ:`w)F8)A}}syB_R]Ur>=3t;pKsBR;m$&+y$}_0U Av University Boise State University Course Organic Chemistry Ii Laboratory (CHEM 310) Academic year 2016/2017 Helpful? 1 Answer. The usually quoted equation is (without the red bits): Almost all sources quote the formation of a basic halide such as Mg(OH)Br as the other product of the reaction. 1 Department of Chemistry and FQRNT Center for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street West, Montreal, Quebec, Canada H3A 0B8. LiCl Enables the Synthesis of Ketones by Direct Addition of
stream Grignard reagents react rapidly with acidic hydrogen atoms in molecules such as alcohols and water to produce alkanes. For the purposes of this page, we shall take R to be an alkyl group. The Grignard reaction consists of two steps. The Grignard reaction is a prominent textbook process to form carbon-carbon bonds. That leaves the carbon atom with a slight negative charge. 0000004509 00000 n
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0 0 Comments %^OtJ1HgqTv1PZe!Om^Y03;>81sW;e&p (1) In this reaction, the so-called Grignard reagent, an organomagnesium species RMgX where R is an organic residue and X is a halogen (usually Cl or Br), promotes the addition of its organic residue to an electrophilic substrate. The carbon-oxygen double bond is also highly polar with a significant amount of positive charge on the carbon atom. This reaction class was chosen because: (1) Grignard couplings are applied in synthetic routes to pharmaceuticals and fine chemicals; (2) The initiation time of the heterogeneous Grignard formation may differ due to varying activation states of the magnesium involved: (3) The preparation of Grignard reagents are highly exothermic reactions. Represented by R-Mg-X, where R is an alkyl or aryl group while X is a halogen, the Grignard reagent easily forms a carbon-carbon bond of 1, 2, and 3 alkyl halides which . Experimental Procedure Grignard Reaction (Malachite Green) Experimental procedure lab write up for grignard reaction. Selective Acylation of Aryl- and Heteroarylmagnesium Reagents with Esters in
P.O. So, I just got to know that trace amounts of Iodine and ethylene bromide is added in the preparation of Grignard reagent from alkyl halides. The reaction of Grignard reagents with O-alkyl S-pyridin-2-yl
The reactions are essentially identical to the reaction with carbon dioxide - all that differs is the nature of the organic product. 0000064068 00000 n
Malachite green is a basic dye, readily soluble in water that possesses antimicrobial properties. 0000073571 00000 n
A Grignard reagent has a formula RMgX where X is a halogen, and R is an alkyl or aryl (based on a benzene ring) group. This reaction was discovered more than a century ago by a French Chemist named Victor Grignard for which he was rewarded a Nobel Prize in 1912. Reaction scheme for the Grignard synthesis of Crystal Violet and Malachite Green. Malachite green | C23H25ClN2 | CID 11294 - structure, chemical names, physical and chemical properties, classification, patents, literature, biological activities . 0000055613 00000 n
via C(O)-N Bond Cleavage under Catalyst-Free Conditions
Preparation of Grignard reagent. Muscular system diagrams - unlabelled, Lecture notes - review of the whole course, Jung Typology and Fruit Classification Essay, Therapy for those with major depression, and other disorder, Health-Illness Concepts Across the Lifespan I (NUR 1460C), Introduction to Human Psychology (PSYC 1111), Child and Early Adolescent Development and Psychology (ELM 200), Business Systems Analysis and Design (IT210), Ethical and Legal Considerations of Healthcare (IHP420), Advanced Medical-Surgical Nursing (NUR2212), Maternity and Pediatric Nursing (NUR 204), The United States Supreme Court (POLUA333), Professional Application in Service Learning I (LDR-461), Advanced Anatomy & Physiology for Health Professions (NUR 4904), Principles Of Environmental Science (ENV 100), Operating Systems 2 (proctored course) (CS 3307), Comparative Programming Languages (CS 4402), Business Core Capstone: An Integrated Application (D083), Final Exams - Selection of my best coursework, ECO 201 - Chapter 2 Thinking like economist part 1 - Sep 9. Grignard Reagents to Carboxylate Anions
Reaction Mechanism [Click Here for Sample Questions] The haloalkanes or aryl halides with sp 3 or sp 2 hybridised carbon atoms when reacted with Magnesium metal give Grignard reagent which is an organometallic compound. 0000050305 00000 n
0000002390 00000 n
Why do Grignard reagents react with carbonyls? Arenes: The Synthesis of 2-Substituted 5-Bromobenzoic Acids
Recall that you studied the reactivity of a series of C-X bonds in Chapter 5. However, if there are traces of metallic . The inorganic product, \(Mg(OH)Br\), is referred to as a "basic bromide" and is a sort of half-way stage between magnesium bromide and magnesium hydroxide. Experimental Procedure Grignard Reaction (Malachite Green), Copyright 2023 StudeerSnel B.V., Keizersgracht 424, 1016 GC Amsterdam, KVK: 56829787, BTW: NL852321363B01, Experimental Procedure: Formation of Malachite Gree, Magnesium (0.080 g, 3.3 mmol) was grinded with a mortar and pestle and added to 4-bromo-, N,N-dimethylaniline (0.500 g, 2.499 mmol), and iodine (one crystal) in a 5-mL, mL) was added to the round bottom flask and magnetically stirred with a stir ba, generated heat that bubbled the ether and changed the solution to a turbid and grass-green color, that lasted 25 sec, before becoming clear and olive-gray, was magnetically stirred and refluxed using a water bath at 35.0 C for 30 min with an appa, (0.10 mL, 0.81 mmol) and diethyl ether (0.50 mL) was added that altered the appearance to a, and solution became olive/vomit colored. Grignard reagents act as nucleophiles. Conventionally, the preformed organometal reagent (organolithium or organomagensium) reacts with carbonyl under air and. Highly Alkyl-Selective Addition to Ketones with Magnesium Ate Complexes
The LibreTexts libraries arePowered by NICE CXone Expertand are supported by the Department of Education Open Textbook Pilot Project, the UC Davis Office of the Provost, the UC Davis Library, the California State University Affordable Learning Solutions Program, and Merlot. Grignard Reagents, aka, Organomagnesium Halides Prepared by Reaction of an Organic Halide and Magnesium metal turnings, usually in an Ether solvent Relative Reactivity of Halides is important RI gt RBr gt RCl gt RF Very few Organomagnesium Fluorides are produced. 0000003347 00000 n
Elementary SchoolMiddle SchoolHigh SchoolHigher Ed. of Aryl Ketones
Market-Research - A market research for Lemon Juice and Shake. The alkyl groups can be any combination of same or different. General Properties of Malachite Green The structure of malachite green is given as follows: I m a g e w i l l b e u p l o a d e d s o o n Structures and properties. * The reactions involving Grignard reagents, as sources of nucleophiles, are usually referred to as Grignard reactions. Privacy Policy. Crystal Violet (Gentian Violet) and Malachite Green are two of the best known of the triarylmethane dyes. You could change the nature of the final secondary alcohol by either: Ketones have two alkyl groups attached to the carbon-oxygen double bond. Continuous Flow
P. Sureshbabu, S. Azeez, N. Muniyappan, S. Sabiah, J. Kandasamy, J. Org. % 0000011756 00000 n
The flask is fitted with a. reagent are carried out with the mixture produced from this reaction. How do you Deprotect trityl group? Malachite green diethylcarbonate methybenzoate Mg HCl HCl Procedure: Complete the synthesis and purification of para-nitroaniline in Week 6. You could obviously get a different primary alcohol if you started from a different Grignard reagent. In addition to being a topical antiseptic, Crystal Violet is especially well . tqH:8&>,fi(Mv1uQj7LwG[ J7t-!w03O.G% b7Qmj+F6%,g)
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. The experiment was first heated under reflux to produce the necessary Grignard reagent as a grey liquid. Lett., 2019, 21, 7851-7856. 3) Reactions of Grignard reagent. Abstract: 4-Bromo-N,N-dimethylaniline underwent a Grignard reaction with diethyl carbonate to produce a type of the tie-dye chemical triarylmethane. Alkynylation, and Arylation of Pyridine N-Oxides
0000056072 00000 n
Both procedures involve preparing a Grignard reagent from 4-bromo-N,N-dimethylaniline and reacting it with an ester (methyl benzoate to make Malachite Green or ethyl carbonate to make Crystal Violet). A. Deichert, L. Kapeniak, R. Lee, J. Harris, P. G. Jessop, V.
Ed., 2004, 43,
For each molecule shown in Fig. A nucleophile is a species that attacks positive (or slightly positive) centers in other molecules or ions. You can't separate it out in any way. 4) Practice questions. The reaction of aliphatic and aromatic secondary and tertiary N-tritylamines with lithium powder and a catalytic amount of naphthalene led to reductive detritylation affording the corresponding amines in good yields. A Grignard reaction involves the use . info@beyondbenign.org, 2023 Beyond Benign. Formally, malachite green refers to the chloride salt [C 6 H 5 C(C 6 H 4 N(CH 3) 2) 2]Cl, although the term malachite green is used loosely and often just refers to the colored cation.The oxalate salt is also marketed. 0000002726 00000 n
organic chemistry 2. mgchit02. ]{|
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L&ih vgrjR+ne=L6/tAilF:6]d&VZoZ *geB2}AslzGRt4Ui `ML~%L2&n61a0c&"fnh?_]4M; Oi(J4r=*d%t|OJkN#
,
u)7AP;R5O5zoLwKss|$xV5>lW|F-"@ English Deutsch Franais Espaol Portugus Italiano Romn Nederlands Latina Dansk Svenska Norsk Magyar Bahasa Indonesia Trke Suomi Latvian Lithuanian esk . Chem. Conclusion In the experiment malachite green dye was. An important aspect of both malachite green and crystal violet is their extensive conjugation, which is responsible for the colors of these two dyes. Dry carbon dioxide is bubbled through a solution of the Grignard reagent in ethoxyethane, made as described above. << /Length 1 0 R /Filter /FlateDecode >> Beyond Benign The halide can be iodine (most reactive), bromine or chlorine (least reactive). The Grignard reaction (pronounced Grin-yard) involves an R-Mg-X, a carbon chain bound to a magnesium halide, typically used to form alcohols by attacking carbonyls such as in aldehydes or ketones. 84, 11823-11838. A typical Grignard reagent might be CH 3 CH 2 MgBr. 20)A'B>b@H; G"a("?:09]p=utJhjP+9qw&x{%t Adv5sCp LShP"^
sW;U(9:# V 1Zxbg/;T2um7[qf/" 211is@f=ODf/bUp%2w.PT
^s*cvoEF=3,Sd;S"m#BLBn l9]NSKt\Af0BtJ( ZX(ubz5Rtj|}H=2JgQs!x'4 Bo[CYV:A5K4\@\hjU5M/G[Ib)?1j:O.? 3333-3336. Any reactions using the Grignard reagent are carried out with the mixture produced from this reaction. Typically, you would add dilute sulfuric acid or dilute hydrochloric acid to the solution formed by the reaction with the CO2. In English, please? Introduction The Grignard reaction is an extremely valuable reaction in organic chemistry because it allows for the formation of carbon-carbon bonds. stream The Grignard reaction is an example of a reaction where anhydrous conditions are critical. Malachite green appears green, so it must absorb red light at 605-700 nm. He was awarded the 1912 Nobel Prize in Chemistry for his work. A. Krasovski, P. Knochel, Angew. Methanal is the simplest possible aldehyde. teacher harriet voice shawne jackson; least stressful physician assistant specialties; grandma's marathon elevation gain; describe key elements of partnership working with external organisations For example: \[ CH_3CH_2MgBr + H_2O \rightarrow CH_3CH_3 + Mg(OH)Br\]. Green Malachite green Crystal violet 2 Bacterial endospores stained with malachite green Bacteria stained with crystal violet 3 Grignard Reactions 4 Grignard Reactions 5 Grignard Mechanism Organic Chemistry, 6 Ed., McMurry, J., Brooks/Cole Belmont, CA, USA, 2004 p. 695. T. E. Hurst, J. A Grignard reagent is an organomagnesium halide having a formula of RMgX, where X is a halogen (-Cl, -Br, or -I), and R is an alkyl or aryl (based on a benzene ring) group. %PDF-1.4 0000009113 00000 n
History & Uses: First made in 1877, Malachite Green has been used primarily as a dye for fabrics, leather, and paper. A Grignard reagent has a formula \(\ce{RMgX}\) where \(\ce{X}\) is a halogen, and \(\ce{R}\) is an alkyl or aryl (based on a benzene ring) group. 0000002065 00000 n
In aquaculture, it is often used as an anti-fungal for eggs in hatcheries, in spite of growing concern regarding . Synthesis of Carboxylic
Assuming that you are starting with CH3CH2MgBr and using the general equation above you get always has the form: Since both R groups are hydrogen atoms, the final product will be: A primary alcohol is formed. 4 0 obj 6 The Reaction (shown for methyl benzoate) 4-bromo-N,N-dimethylaniline . 0000064706 00000 n
Wilmington, MA 01887 Grignard reagents are made by adding the halogenoalkane to small bits of magnesium in a flask containing ethoxyethane (commonly called diethyl ether or just "ether"). Org. Download Lesson CS_Greener_Grignard.pdf The Barbier reaction is an organic reaction between an alkyl halide and a carbonyl group as an electrophilic substrate in the presence of aluminium, zinc, indium, tin or its salts. The nature of this bond is described in detail elsewhere on this site. This is the reason that everything has to be very dry during the preparation above. ^1MFui*s~Z4feL/_ ]ZA 9B'l(NHvP9mj96s)VQ 0000001376 00000 n
0000008012 00000 n
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This specific triarylmethane produces a vivid crystal violet color when dyed. The greener approach reduces the use of undesirable ethers, and avoids the use of hexanes, and magnesium. x\tG!P*AZ!f|G m+Eb^R|!p[c Doc Preview. status page at https://status.libretexts.org, changing the nature of the Grignard reagent - which would change the CH, changing the nature of the aldehyde - which would change the CH, changing the nature of the ketone - which would change the CH. 1). Cross), Chemistry: The Central Science (Theodore E. Brown; H. Eugene H LeMay; Bruce E. Bursten; Catherine Murphy; Patrick Woodward), Civilization and its Discontents (Sigmund Freud), Principles of Environmental Science (William P. Cunningham; Mary Ann Cunningham), Campbell Biology (Jane B. Reece; Lisa A. Urry; Michael L. Cain; Steven A. Wasserman; Peter V. Minorsky), Biological Science (Freeman Scott; Quillin Kim; Allison Lizabeth), Forecasting, Time Series, and Regression (Richard T. O'Connell; Anne B. Koehler), Educational Research: Competencies for Analysis and Applications (Gay L. R.; Mills Geoffrey E.; Airasian Peter W.), Psychology (David G. Myers; C. Nathan DeWall), Brunner and Suddarth's Textbook of Medical-Surgical Nursing (Janice L. Hinkle; Kerry H. Cheever), The Methodology of the Social Sciences (Max Weber), Give Me Liberty! 0000069411 00000 n
for liquid assisted . Despite significant utility . The Grignard reaction ( French: [ia]) is an organometallic chemical reaction in which alkyl, allyl, vinyl, or aryl - magnesium halides ( Grignard reagent) is added to a carbonyl group in an aldehyde or ketone. 0000077824 00000 n
A LiCl-Mediated Br/Mg Exchange Reaction for the Preparation of
0000009976 00000 n
That leaves the carbon atom with a slight negative charge. General Reaction between Grignards and carbonyls, Reaction between Grignard reagents and methanal, Reaction between Grignards and other aldehydes, The reaction between Grignard reagents and ketones. The Grignard Reaction is the addition of an organomagnesium halide (Grignard reagent) to a ketone or aldehyde, to form a tertiary or secondary alcohol, respectively. X.-J. On3O&@##t(Pr- Grignard Reagent Preparation and Reaction: READ THIS HANDOUT CAREFULLY! Sodium Methyl Carbonate as an Effective C1 Synthon. 9, 1335-1337. The Grignard reagent is represented as R-Mg-X, where. Wang, L. Zhang, X. However, it is still highly desirable . Acids, Benzophenones, and Unsymmetrical Ketones
One-Pot Access to 1-Azaspirocyclic Framework
Snieckus,
But I don't understand their need. Show calculationHere was the procudure: Weight out 200 mg of magnesium turnings and polish them thoroughly with the polishing cloth to expose fresh surface area. The reaction is similar to the Grignard reaction but the crucial difference is that the Barbier reaction is a One-pot synthesis whereas a Grignard reagent is . In the first, you get an addition of the Grignard reagent to the carbon dioxide. The stoichiometric reaction of Grignard reagents with carbonyl compounds is a common Cross), Chemistry: The Central Science (Theodore E. Brown; H. Eugene H LeMay; Bruce E. Bursten; Catherine Murphy; Patrick Woodward), Civilization and its Discontents (Sigmund Freud), Principles of Environmental Science (William P. Cunningham; Mary Ann Cunningham), Campbell Biology (Jane B. Reece; Lisa A. Urry; Michael L. Cain; Steven A. Wasserman; Peter V. Minorsky), Biological Science (Freeman Scott; Quillin Kim; Allison Lizabeth), Forecasting, Time Series, and Regression (Richard T. O'Connell; Anne B. Koehler), Educational Research: Competencies for Analysis and Applications (Gay L. R.; Mills Geoffrey E.; Airasian Peter W.), Psychology (David G. Myers; C. Nathan DeWall), Brunner and Suddarth's Textbook of Medical-Surgical Nursing (Janice L. Hinkle; Kerry H. Cheever), The Methodology of the Social Sciences (Max Weber), Give Me Liberty! x\yS*5[
hqhKsCDQ6y$VyA4'4gr/}xn]_vfoPnzUY?]n]LSnvCU=J-qSUnvxP`U}"F m] halide (Grignard Reagent) to a ketone or halide, to form a tertiary or, secondary alcohol. Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents
All Rights Reserved, Green Chemistry Teaching and Learning Community, Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. %PDF-1.3 Saturated sodium chloride aqueous solution can . Solution was transferred to a 50-mL, in an ice bath for 2 min before hydrochloric acid (0.5 M, 0.30 mL) was added, which af, malachite green (0.90 mL, pH 4) as a turbid, dark blue/green solution: UV, Business Law: Text and Cases (Kenneth W. Clarkson; Roger LeRoy Miller; Frank B. R = alkyl / aryl / alkenyl / allyl group. . A one-pot, three-step protocol for the preparation of Grignard reagents from organobromides in a ball mill and their subsequent reactions with gaseous carbon dioxide (CO 2) or sodium methyl carbonate providing aryl and alkyl carboxylic acids in up to 82 % yield is reported.Noteworthy are the short reaction times and the significantly reduced solvent amounts [2.0 equiv. It has been used as an effective compound to control external fungal, bacterial, and protozoan infections of fish, and successfully used as a treatment to control fish saprolegniosis and as a prophylactic treatment to protect fish eggs from infection (Ali et al., 2015). The Grignard reaction is an organic reaction used to produce a variety of products through the reaction of an organomagnesium compound, also known as an electrophilic "Grignard reagent," followed by an acidic reaction. To ensure optimization and safety of Grignard reactions in research, development and production, in situ monitoring and understanding reaction heat flow is important. Weigh magnesium powder (50 mg, 2 mmol) and add it to your reaction vessel. Reaction usually in Et 2 O or THF followed by H 3 O + work-up Reaction type: Nucleophilic Addition. HVn1+xLQEM@(zHrW33$}#7HNQZSF}Brc*3^W;}7-Zv?1kM-:B#t/&c2gg4N qN'IjQ6
\}\?Znvp+G[. 5 0 obj The reaction product is a secondary or tertiary alcohol. A Grignard reagent is formed by reaction of magnesium metal with an organic halide in diethyl ether. The simplest one is propanone. Everything must be perfectly dry because Grignard reagents react with water (see below). [ 6] The next biggest aldehyde is ethanal. These alkyl, vinyl or aryl magnesium halides are referred to as Grignard reagents. Crystal Violet (2), whereas addition to methyl benzoate followed by acid hydrolysis could lead to the dye Malachite Green (3). Use the direction out of the page as the positive direction and into the page as the negative direction in your answer. K. Menzel, L. Dimichele, P. Mills, D. E. Frantz, T. D. Nelson, M. H. Kress, Synlett, 2006,
Grignard Reaction - ChemConnections. 0000063863 00000 n
Examples include: The reactions between the various sorts of carbonyl compounds and Grignard reagents can look quite complicated, but in fact they all react in the same way - all that changes are the groups attached to the carbon-oxygen double bond. The reaction is considered an important tool to form carbon-carbon bonds. P. Cali, M. Begtrup, Synthesis,
Organomagnesium Reagents
Grignard reagents react with water to produce alkanes. Iodine "activates" magnesium so it can form a Grignard reagens. xb```f``V @Q
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{0pq5=; Again, think about how that relates to the general case. For the purposes of this page, we shall take R to be an alkyl group. Calculate the net magnetic field at a point midway between the wires. 2002, 1115-1120. This MUST be read before entering the laboratory in addition to Chapter 19. . One of the key uses of Grignard reagents is the ability to make complicated alcohols easily.
( a) Strict anhydrous conditions for the Barbier-Grignard-type reaction. -6Mr>Y"e>>(
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9?sasgOhbnIblPNl^ 3byv4H3hpU.YEVTVbZ173&h_qv 6of Grignard reagents react with dry ice (solid CO 2) followed by aqueous acid work-up to give carboxylic acids. xL0_r#Gj6} vIMQWU1DnTz#$/W`(([I^e(ZcjO NWZ~hh}
_f w*77=KxEL7X!\H No, pure malachite $\ce {Cu2CO3 (OH)2}$ usually doesn't produce hydrogen because it is a copper carbonate. 0000001729 00000 n
Hydrogenation Reactions. Summary. {NgCPcQ}08HWYZ8=UU2 ^ q~;B}16^w1bx/#z "sWjs5VT\TMJ\exoX.>]jl4d` }KRa\/y[B7~E)h]}~
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1?OKrn&]jF)#YIo&l=7!Gc#~MJ0fH F@=jqs 9.>+iy*R^4y$hwj,)-u-tn_6$O`I+P:L%Jt>3_E\LWs_s=\HN{x.(0ulG,?;hV
!s~UKvW1BcS}wh{|?F4"e_w referred to as a "basic bromide" and is a sort of half-way stage between magnesium bromide and magnesium hydroxide. The Grignard reaction requires absolute anhydrous conditions. x][u~_yIa]$4s_\Er1DnI,?\-+h+N]so}/{us_|ce|47]mU]L7,m %PDF-1.3 With the . 0000001667 00000 n
Obtain 3 mL of anhydrous diethyl ether from your GSI in one of the oven dried dram vials.
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Books Featured On Cbs This Morning Today, Florida Medicaid Provider Master List, Why Did Money Develop In Agrarian Societies, Robert Stack Child Kidnapped, Articles G