All right, good morning now. Well, I feel we've now come to a very nice place in the course. You've been working extremely hard. We've just gone through what I said I felt was really the intellectual pinnacle of sophomore organic chemistry. We've been through a very rich collection of carbonyl chemistry. You've experienced it with the enolate and enol chemistry on this quiz and in this week's discussion, you'll be getting reinforced some of the things we talked about in class last week with all of these wonderful reactions, the Aldol reaction, the Claisen reaction, the Michael reaction, the Robinson annulation reaction. All this ability to recognize interrelationships in a molecule, beta hydroxy carbonyl compounds, alpha, beta unsaturated carbonyl compounds, 1, 3-dicarbonyl compounds, 1, 5-dicarbonyl compounds, and cyclohexenones. And so at this point, at least as far as the lecture part of the course, that's behind us and now you're going to be working on that and reinforcing these concepts through the discussion section and the homework problems and our last quiz. So we come into the last few chapters of the class and I think this is a fun point in the course. We've done a lot of hard work. We're still going to have a lot of nice ideas. This week, we're going to be talking about the chemistry of amines and in some ways in a course like this, this is a neither here nor there chapter of the class because you've gotten a big richness of the chemistry of amines already. You've learned about their reactions to make amides. You've learned about their chemistry as acids and as bases. You've seen some generation of amines when you studied aromatic chemistry and electrophilic aromatic substitution. So in a way, this week's chemistry is a bit of a refrain. We'll see a few new cool reactions, some cool syntheses, a few neat mechanisms. The next week, we're going to come into the chemistry of carbohydrates and carbohydrates are going to bring in some carbonyl chemistry. We'll see chemistry of acetals and their formation and their breakdown. We'll see some chemistry of enol, keto, tautomerization and some acid catalyzed reactions. We'll come way back to ideas of stereochemistry. We got a little bit of this as we talked about some of our some of our aldol chemistry and we reviewed some ideas of enantiomers and diastereomers and you'll get more of that. I'll try to bring in some of the molecular modeling that we did if things work out right. Maybe I'll ask you to bring your computers into class. I'll think about that next week but be prepared to maybe bring your laptops in next week. And then the final week of class looks like it's going to be a big thing because we've got a couple of chapters. I want to pick out a few highlights. I guess there's chapter, think if I remember the numbers, there's chapter 28 and I may have the numbers wrong but there's a chapter on amino acids, peptides and proteins and some of this is going to be redundant with your biochemistry chapters. I want to focus on one aspect of that which is another real intellectual pinnacle of organic chemistry and that is the solid phase synthesis of peptides and that'll bring in some nice reactions. You'll see amide bond formation. You'll see some concepts of aromaticity and stability of anions and you'll see a really profound idea of being able to build up molecules repetitively step after step, biologically important molecules, molecules that are all sorts of things, hormones that lead to uterine contractions in pregnancy and birth and so forth and this was one of the intellectual triumphs. And if everything works out in our timing, the last and I'll give you a selection from that chapter from the amino acids chapter selection to work on. And if everything works out right in our very last class, one of my big laments in organic chemistry is that a lot of the really modern concepts, I mean some of the chemistry you're going to see goes back more than 100 years. We've talked about some of this chemistry in some of the reactions we've discussed like the aldol reaction and the Claisen reaction. But if everything goes right in the last lecture, we'll get just a taste of organometallic chemistry, not Grignard, I mean we've already done Grignard chemistry but chemistry in which metals can act as templates to form carbon-carbon bonds. So we'll see how things go. So today I want to start by talking about amines and talking about their properties and their synthesis and amines are really cool molecules and really important biologically. They're present in so many biologically active natural products. Many of these are called alkaloids and are produced by plants and I want to draw out two of these molecules and I want you to draw along with me. They look really hairy so I'm going to draw at least the first one I'll draw slowly. It looks really, really hairy. So we're going to start by drawing a benzene ring like so and we're going to connect that to a cyclohexane ring. We'll make it a cyclohexane ring. For those of you who, well for everyone here you'll know my handwriting's no great shakes and yet a few simple tricks like being able to draw a hexagon or being able to draw a zigzag line really help. We're going to connect these two rings together by way of an ether linkage from the benzene to the cyclohexane ring and I'll show some stereochemistry over here. We'll put on a couple of hydroxy groups, one on the benzene ring and of course there's no stereochemistry on that hydroxy group and then we'll have another hydroxy group going down. In other words in the stereochemistry going down. We'll draw one more six-membered ring here. So far everything's pretty easy to visualize. Now we've got some overlapping bonds so I'm going to put a bond, a wedge, a line coming out of the blackboard to a nitrogen here and again if you're good at drawing hexagons you can do a lot of things and then fake the rest. So we'll have another bond off of the nitrogen. Going to show a bond coming out over here like so. We'll connect that over to the bond to the nitrogen so we're crossing. If you want to get fancy and people are really good can do this beforehand if they just plan their drawings. I'm not really good at drawing. You'll put a little break in there to help indicate that we're going above. So that doesn't mean a broken bond. It's sort of a way of drawing perspective. So you've got that. We'll set, I'll show you some stereochemistry over here, a hydrogen and we'll finish our molecule off by putting a methyl group on the nitrogen. Does anyone know what this molecule is? Morphene. Who said that? Good. Morphene, good for you. How do you know? What's that? I looked at the chapter. Ah, did they? Okay, so I didn't see morphene in the chapter. I saw, okay, so great, great. And this is a really important molecule in organic chemistry. And when I teach my graduate level spectroscopy course, I tell students that it took chemists 50 years to determine the structure of morphene. And now this is something that our graduate students can do in the course of an afternoon. I didn't see morphene, but I saw at least one related compound in the chapter. So morphene is part of a family of what are called alkaloids. Alkaloids are nitrogen-containing compounds produced by plants. Morphene in particular is an opioid. It's produced by the opium poppy. Incredibly important in pain relief after, you know, all of decades upon decades of pharmaceutical research when you have really bad pain, terminal cancer pain and all sorts of horrible things. Morphene is still the drug that is given. Of course, as an opioid, it's an addictive drug, but, you know, at some point if you have terminal cancer, it doesn't matter. Many of the synthetic drugs that also work on pain bind to the same receptor in the brain and it's really hard to separate pain relief from the ability to get addicted. The one I saw in the chapter, I've never taken morphene myself as a drug or in any other context, the one that I've seen in the chapter has a methoxy group over here. If you have instead of a hydroxy group, you have a methoxy group, that's another opioid. It's codeine, it's great cough medicine. I've taken that one. It's potentially abusable, potentially addictive. Morphene and opium, of course, are widely sought after, I mean, we've got tremendous trouble with drug trade from Afghanistan and so forth where poppies grow, but what really makes morphine unfortunately valuable as a street drug and highly sought is its diacetylation. In other words, if you take morphine and you treat it with acetic anhydride, you get the diacetate over here and over here, an acetoxy group. Anyone know what that drug is? Heroin, very easy to make heroin. So, as I said, morphine is an amine and it's specifically a tertiary amine to nitrogen with three groups on it. I want to draw one other alkaloid. Your textbook really goes to town talking about everything from neurotransmitters like dopamine and serotonin to nicotine, another highly addictive compound to all sorts of other molecules, spermine and spermidine. So, I'll draw one other molecule. It's based on a bicycloheptane skeleton. So, I'll draw out that skeleton. I'll show you a little trick of mine as well.  So, the one other bicyclic structure that I like to be able to draw is norbornane. And if I can draw this, it's a cyclohexane in a boat with a bridge. If I can draw that, I can sort of fake everything else because the structure that I'm drawing now is basically norbornane with one extra methylene over here and so you can sort of fake it. And we have in the bridge position a nitrogen. It's a methylated tertiary amine group just like we have in morphine. I don't think this one's in your textbook. We'll have a methyl ester group over at this position. We'll have a benzoyl group over at this position. Anyone know what this molecule is? Cocaine. I have had that one medicinally. When I was in college, I used to get terrible nosebleeds and so to treat it, apparently the treatment involved some silver nitrate up your nose but before that, it was preceded by some cocaine up your nose. That was another one I used in my graduate level spec class. One of my colleagues is authorized to have a bottle of cocaine for research purposes. I was very happily walking around with a one gram bottle of cocaine that was to become the final exam for our graduate students. So all of these compounds and you can see how and one of the cool things about this is by this point in the course, you should be good enough with functional groups so when I go ahead and show you a big hairy molecule like morphine and I say, yeah, we treat it with acetic anhydride even though maybe your textbook examples might have included treating isopropanol with acetic anhydride to get isopropyl acetate, you can understand that these same principles of reactivity apply. You've got a basic amino group in there. The amino group is going to behave as a base. You can extract alkaloids into aqueous acid solution by protonating them and then you can go ahead and remove various impurities and then go and treat with base and extract back into organic solvents so you can recognize functional groups. We have an ester group over here. Okay, so the group there is a tertiary amine. I suppose the group is a tertiary amino group but I'm going to write tertiary amine and just write a generic structure R3N. And I'm not going to be so fussy as to go R1, R2, R3N but of course you can have three different groups. We've used tertiary amines as reagents. You've used triethylamine as a base. Tertiary amine of course has three different carbon atoms attached to the nitrogen atom and a lone pair as well on the nitrogen. A secondary amine, again I'm not going to be so fussy as to say R or R prime or R1 or R2 but you have two alkyl groups, two R groups on the nitrogen, two carbon containing groups. You've already encountered, we've used certainly again and again in our enolate chemistry. We've used this amine. We've used diisopropyl amine, the secondary amine. See primary amine, by the way you'll see people write 1-0 for primary, 2-0 for secondary, 3-0 for tertiary. That's fine too. I don't know, for primary amine of course we're talking RNH2 here so I'll give us an example of methyl amine CH3NH2. Now of course one thing to keep in mind is there's a fundamental difference between talking about amines and talking about alcohols. When we use the notation primary, secondary, tertiary for alcohols, of course we're talking, we always have NOH right? When you go ahead and have two R groups on an oxygen that's an ether, it's a different class of compounds but with alcohols you'd say okay ethanol is a primary alcohol, isopropanol is a secondary alcohol, tertbutanol is a tertiary alcohol so that's one thing that's different. All right, I want to maybe show us a couple of aryl amines so these examples here are all alcohol amines and there's some real differences in reactivity and even differences in the structure and bonding of aromatic amines and aliphatic amines so I'll just show you a couple of aryl amines. So because the chemistry of amines is so old, so many of these compounds have common names that are used in preference to maybe a more systematic name. In fact, the common names have really gotten wrapped into these systematic names so you wouldn't call that compound, no chemists would call that compound phenylamine or aminobenzene, they'd call it aniline and I guess somebody could call it aminobenzene, certainly if it's a substituent you'd call it, I'll show you that in a second but I'll just give you one other idea for substitution. I don't think we're going to be as systematic maybe in our discussion of nomenclatures we've been with some of the other compounds in part because amines people differ so much from systematic nomenclature and how they refer to them. So if we're going to refer to substituents on the nitrogen, we'll just put the capital letter n, if you're type setting it you'd set it nitallic. So this compound has two amine, two methyl groups on nitrogen so this would be nn dimethylaniline. And maybe I'll give you one more example. So if you have, remember I talked about substituents and I said okay if you have like a carboxylic acid in general things are substituent so for example if you have a hydroxy group and a carboxylic acid and a long chain alcohol group you'd call it a hydroxy acid, a beta hydroxy acid or you'd say three hydroxy propanoic acid. Similarly in terms of ranking and in terms of priority of the amino group is pretty far down the totem pole so if you have a ketone or you have an aldehyde or you have an acid in the molecule or a nitrile you're going to be naming it as an amino substituted molecule. So this molecule here we don't name as an aniline, we call this P-amino benzoic acid. So one of the things that's really defining about amines as a matter of fact is probably the first or second word that I would think about when I think about amines is their basic. And we probably also think of them as being nucleophilic. We've already seen lots of their chemistry as bases and it's a good chance to review and also to straighten some concepts in our mind. So we always think of basicity, we think of the PKA of the conjugate acid as a measure of basicity. So the PKA of the conjugate acid of an alkylamine something like triethylamine or diisopropylamine or methylamine. The PKA of the conjugate acid, I'll just write it in generic form and sort like this. The PKA is on the order of 10 to 11. There are a few numbers you should keep in your head, that's one, you can keep 10, you can keep 11, you can keep both, doesn't much matter. Now what a lot of students find confusing and I hope, I hope, I hope by this point you don't. But it's always good to have a reminder to get things in your, straight in your head is that if you have ammonia or you have a primary or secondary amine, all of these compounds are amphoteric. And it's very important to keep this straight in our head. So when we talk about diisopropylamine and we talk about making LDA, we're thinking about a completely different equilibrium. So we know diisopropylamine, when we think about making LDA, we say, oh, the PKA is about 40. And of course what we're doing and I hope, I hope, I hope by this point that you're on top of this is we're thinking about two different equilibria. One in which the amine is acting as an acid. So when you take diisopropylamine and say butyl lithium, we have an equilibrium that lies so far to the right that for all intents and purposes, I barely think of it as an equilibrium where we get diisopropylamine and butane. And here what we're saying is an acid, PKA 40, reacts with a very strong base to give a slightly less strong base and a conjugate acid of butyl lithium is butane, PKA about 50.  So now again you have this equilibrium that lies so far to the right that I'm not even bothering to write it as an equilibrium where now we're talking about say, I'll give you an exact number, it happens to be 11 in this case but again 10 or 11 doesn't matter and so that equilibrium lies way, way, way to the right. Now, one thing that's important to keep in mind in avoiding confusion is there's a huge difference between a means and a means. In a means, you have a nitrogen that's pyramidal, so this isn't a mean, it has a lone pair. If it's an alkyl amine, it has a lone pair that's in an sp3 orbital and for an alkyl amine it's not participating, the electrons are not participating in any significant resonance and so that lone pair is available to protonate. Now, where a lot of students get confused the first time around is thinking in comparison to amides and so I'll take say a generic amide but of course it could be in this case dimethylacetamide. Now, the huge difference is yes, you have a lone pair on that nitrogen but that nitrogen is tied up by resonance so it's not available. The lone pair is not available. If I had to characterize amides I'd say simply not basic. It's not exactly true. They're basic but very weakly basic, pKa sort of into the negative range, negative one for the conjugate acid but they're not basic on nitrogen, it's the lone pairs on oxygen that actually protonate. That lone pair is tied up by nitrogen by resonance and in fact because you have a good degree of double bond character for all intents and purposes your lone pair really is more like sp2 hybridized and your nitrogen is almost planar. I'll say a little tilde, approximately planar, just think of it as planar and think of it as approximately sp2 hybridized. So I want to make a comparison between amines like disapropyl amine and triethylamine and methyl amine and ammonia of course. I mean it's not an amine but it's basically the parent of the same family much as water is the same parent, is the parent to alcohol and amines that have aromatic groups in them. So when I drew aniline we also have a situation that in some ways is like our amide. You've got a nitrogen with a lone pair but that lone pair is participating in resonance. The lone pair is donating into the aromatic ring. When you learned about electrophilic aromatic substitution you learned that amino groups were ortho power directors that they were pushing electron density to the ortho and power positions of an aromatic ring and then in turn able to stabilize a positive charge that formed during the electrophilic aromatic substitution reaction. So the lone pair is tied up by resonance and it's sort of halfway between the degree to which it's tied up by resonance and an amide and the degree to which it's available in a simple aliphatic amine, a simple alkylamine. The pKa of the conjugate acid, so the pKa, so this is an aryl amine. Aryl is just a fancy word for aromatic. And the pKa of if you want to write it as AR NH3 plus, the conjugate acid of a generic aryl amine could be aniline, vary a little bit by substituents there. We're talking about five, whoops, not 55. So in other words, not as non-basic as an amide but not nearly as basic as an alkylamine. There are other nitrogen containing organic compounds. There are all sorts of nitrogen containing heterocycles and some of them you should already know from discussion of aromaticity and structure and bonding. So for example, pyridine is the nitrogen analog and I'll draw the lone pair here just to be very explicit. So this is pyridine. We've been using it as a reagent in some acylation reactions. Pyridine is the nitrogen analog of benzene. The nitrogen is participating in the aromatic ring system and instead of having a CH group, it has a lone pair of electrons. The lone pair of electrons is sp2 hybridized. And remember, when you use more S character, you hold your electrons closer to the nucleus. That makes them more stable, less willing to share. So when you use more S character, your lone pair is less available to bond to a proton.  So the pKa of pyridinium, the conjugate acid of pyridine, the pyridinium ion is also about pKa of 5. I want to give you one other nitrogen-containing heterocycle and it's one that you've probably seen before in your discussion of aromaticity and this nitrogen-containing heterocycle is pyrrole. Now, pyrrole is another one I think that beginning students often find confusing.  It looks like it ought to be basic. And that lone pair of electrons ends up being part of the aromatic pi system. As a result, if you protonate it, you're going to give up a ton of resonance energy. That lone pair, just like the lone pair in amides, is for all intents and purposes not basic. Pyrrole can protonate, but when it protonates, it actually ends up protonating on carbon, not on nitrogen. So thoughts or questions at this point? Yes. Why can they, if they're all, so, okay, when we're talking about basicity, this is the thing, what I was talking about with the concept of amphoteric. When you're thinking about how basic something is, you have to throw a switch in your mind and say, that means I need to think about the conjugate acid. When you're talking about how acidic something is, so we're not discussing the acidity of pyrrole, then you're thinking about, okay, what are we doing to give up a proton and form the conjugate base? So remember, in your mind's eye, when we're thinking about the basicity of pyrrole on nitrogen, you're thinking about this species here with two protons, and you're saying, oh my goodness, I've had to give up all of that resonance energy, all of that aromaticity, that's terrible, that doesn't form. Pyrrole doesn't have quite as much resonance energy as benzene, so you don't have, it's not quite as bad to protonate on the ring, and it's very reactive in electrophilic aromatic substitution. Now, okay, so as I said, to me, basicity really characterizes amines. The other thing, if I had to think about amines and sort of say what do I think about amines, I'd say, to some extent, I think of them like alcohols, but less so in everything, except basicity, and I'll show you what I mean in a series of discussions of properties in spectroscopy. So amines are kind of like alcohols, but less so. They're less polar than alcohols, they're dipole interactions or weaker, they're hydrogen bonding is weaker, so I'll say less polar than alcohols and less hydrogen bonding than alcohols. They're few compounds that's kind of worth having in your head as a reference point. Methanol or ethanol are sort of good ones. You've probably worked with them in laboratory. You should know that methanol is a liquid. If you don't know the exact boiling point, you at least would know it's a volatile liquid. It boils lower than water. It happens to have a boiling point of 65. It's toxic. It's a lower boiling point than ethanol, but not that much lower, and unlike ethanol, it causes blindness, permanent blindness, not being blind drunk. So if I compare, say, methyl amine, which you'd say, okay, it's about the same weight. It should have about the same, it's about the same size. It should have about the same Van der Waals interactions, and so then differences are going to be in hydrogen bonding and dipole-dipole interactions. So methyl amine, by contrast, is a gas. In other words, the molecules don't have enough interaction with each other to cohere into a liquid at room temperature. It's a gas until you cool it to negative 6 degrees at atmospheric pressure, or of course, if you have it at higher pressure, it's a liquid. Now, by contrast, again, the simple compounds, if you look at something about the same size, if you look at ethane, again, it's just too big, you know, two heavy atoms, two second-row atoms, and it's about the same size and the same weight, but you don't have dipole interactions, you'll have Van der Waals interactions, you don't have hydrogen bonding. And ethane, of course, is a gas. Its boiling point is negative 88 degrees, so by the time you're down to a molecule of that size, you really have to go cold. So you look at this and you'd say, well, okay, methylamine is like halfway between methanol and ethane in terms of its interactions. It doesn't hydrogen bond as much. It doesn't participate as in as many dipole-dipole interactions or as strong dipole-dipole interactions. And not surprisingly, that tracks with electronegativity because electronegativity is basically a statement of the property of elements. And so nitrogen is less electronegative than oxygen. Nitrogen, the electronegativity is 3, 3.0, and oxygen, the electronegativity is 3.4. In other words, the nitrogen pulls the electrons away from the hydrogen less, so the hydrogen bond less. You've got smaller dipoles in the molecule. And so for both reasons, that shows. And you can see this, so if you want to now separate out the hydrogen bonding component from the dipole-dipole component, I'll give you another comparison. So we'll look at trimethylamine, CH3, 3 nitrogen. So that's a gas. It's boiling point, though, is just above freezing of water. It's boiling point is 3 degrees. And if we compare it to something comparable in size to isobutane, now we have a lower boiling point, although not that much lower. So CH3, CCH is isobutane, virtually the same size and shape as trimethylamine. And the boiling point, it's also a gas. The boiling point is now negative 12 degrees. So you can look at that and say, yeah, okay, we've got dipole-dipole interactions in trimethylamine, and those raise the boiling point a little bit over isobutane that just has van der Waals interactions. But it's not a huge difference. All right, in so many ways amines are lesser versions of alcohols, and it's probably in terms of what you see in the spec part of the course you get for IR. You're not going to see it, but when we actually look at real IR spectra, you see it. So in the IR spectrum, you have an NH stretch, and the NH stretch is essentially at the same place as alcohols. It's that region above 3,000, that region kind of around 3,300 to 3,500. So the NH stretch, I'll say it's like the OH stretch. In other words, you'll typically see from your textbook you can use 33. In my graduate course, I give more detail, but you can use 3,300 to 3,500 wave numbers. But when you look at an actual spectrum, what you see is the band's a lot weaker. Now, you're not going to see this, but maybe you will if there's some spectra in the humor. But what I mean is an alcohol really stands out. It really yells at you. An amine kind of whispers at you. You can look with a small amine, and you go ahead and you say, oh yeah, I can see it. But by the time you get to a big compound with an amino group in it, it's very, very weak. If you have a primary amine, you'll actually see two bands that correspond to an asymmetric and a symmetric stretch. The other thing, and your textbook doesn't mention this, right, I always, when I read an IR spectrum, I generally look at the region from about 1,600 on up, right at the very bottom of that region. There's an NH band, and so it's right at about 1,600. And it's just below. And the thing that I'll mention to you since you may see in your lab course, or maybe you'll see it in one of your homework course, homework problems, it's just below where the carbonyl group occurs. So the carbonyl group, we said normally about 1,700, but then we said for amids, it can be about 1,650 or 1,660 or so. And this is just on the lower edge of that. So when you're reading a spectrum, you want to make sure you don't mix it up. All right, NMR spectra, again, this idea of kind of like an alcohol, but less so, comes up, or at least it's how I organize it in my own thinking. I'll show you what I mean. To me, when I'm thinking about an alcohol, I'm normally thinking about the hydrogens on the carbon next to the oxygen, and so I'm thinking, all right, that's sort of 3 to 4 ppm. That would be kind of a range if you want to keep one number in your mind. I can give you a more detailed number. But when I'm thinking about an amine, and again, I'll just sort of write a generic structure. That nitrogen's less electronegative. It's pulling electron density away from that hydrogen less, and as a result, it's not shifting it as far downfield. So generally, the hydrogens alpha to an oxygen and an alcohol are going to be kind of in the 3, 3.5 ppm range. In an amine, it's going to be in the sort of 2 to 3 range. Your textbook gives 2.3 to 3, which I think is a good sort of general assessment, but remember, those are always loose. In other words, dimethylamine is 2.3 ppm. By the time you go to a more sterically congested group or more substituted group like diisopropylamine, you're more toward 3 ppm. The NH, so when we talked about alcohols or when you talked about alcohols in spec, you said they're all over the map due to hydrogen bonding. And it's kind of the same thing about the NH group. Your textbook gives 0.5 to 5 ppm, and that's a good general start unless you're an aralamy like an aniline, in which case it's going to be a little bit further down. But the NH is often very broad and hard to see. And so for those of you who go beyond the textbook course, I'll say often broad and hard to see.  I don't see an NH, and in fact, it's just that the NH is so far broadened out. In the C13 NMR and the carbon 13 NMR spectrum, again, we're sort of like an alcohol but less so. In other words, for an alcohol I think for the oxygen bound to carbon, oh, about 50 to 70 ppm. And it's pretty characteristic because by that point, you're down far enough in the carbon, you're away from everything else. For an amine, you're really not that well separated. The carbon that's bound to a nitrogen is in about the 30 to 50 ppm range, which isn't that far from other sorts of carbons that may not have electronegative substituents on them. All right. So that kind of gives the quickie view of the spectroscopy of amines and their properties. And as I said, a lot of what we're going to see particularly today is a refrain of some of the chemistry you've seen of amines before like in the aromatic chapter. So in the synthesis of amines by way of a quick review, you'll learn that nitration, that electrophilic aromatic nitration was a very common reaction in a way to substitute an aromatic group. And the nice thing is it's really, really easy to reduce the nitro group. And your textbook gives three different ways, but I can give you a hundred different ways to reduce the nitrogen, the nitro group, down to an amino group. So your textbook taught you that catalytic hydrogenation with hydrogen and palladium on carbon can reduce the nitrogen or you can use a metal, metals or reducing agents in general. Metals want to go to metal cations, they want to give up electrons. So iron and hydrochloric acid or tin and hydrochloric acid, these are three conditions from your textbook and they're all good ways to reduce the nitro group on an aromatic ring down to an amino group. Allophatic nitros are a little harder to reduce, but they can be reduced by catalytic hydrogenation as well under slightly different conditions. You've learned that lithium aluminum hydride reduces everything and anything. We saw that all the carbonyl groups got reduced down, esters go to alcohols, carboxylic acids go to alcohols, ketones and aldehydes go to alcohols. And the odd ball in the chemistry of lithium aluminum hydride was that because it's hard to kick out the nitrogen in the reduction process, you reduce, you add hydride, you get a tetrahedral intermediate, you end up forming a bond to aluminum, your nitrogen kicks out the oxygen, you add another equivalent of hydride. And so lithium aluminum hydride, LIALH4 followed by an aqueous workup reduces most amides down to amines. Lithium aluminum hydride reduces just about everything except carbon-carbon bonds in general. And so nitrials also get blasted down to amines. So if I take, say, benzonitrile and I subject it to the same conditions, I'll just write a ditto mark here, you get phenylethylamine. So immediately you can start to think about ways of making amines where you could start with a carboxylic acid, make an amide, reduce the amide to an amine, or start with an alkyl halide, do an SN2 displacement with sodium or potassium cyanide to get a nitrile and then reduce the amine to a primary, reduce the nitrile to a primary amine. All right. So one of the other analogies I like to make because nitrogen and oxygen are very similar in a lot of their structure and bonding. Nitrogen, of course, forms three val, has three valencies. Oxygen has two valencies, so there are differences. Nitrogen is less electronegative than oxygen, so compounds with bonds to nitrogen end up being less electrophilic with double bonds to nitrogen. And yet in many ways you can see similar reactivity. So in the broadest sense of abstraction, if we have some carbonyl compound, a ketone or aldehyde, and in the broadest sense of abstraction, if we envision adding a hydride nucleophile, and of course you can't go and get hydride any more than you can go ahead and get carbanion, but if we take some hydride source, I'll write this as hydride source just so you have it for your notes. Of course, you reduce after some sort of aqueous workup, you reduce, and again we're talking very broad abstractions here, you reduce your ketone to or your aldehyde to an alcohol. Now, by a similar token, if we have a carbon nitrogen double bond of an imine, an imine of a ketone or an aldehyde, and again we have some type of hydride source, H minus in quotes, you reduce your imine to an amine like so, very much by analogy. Now, this chemistry often gets put together where one can carry out the formation of an imine and the reduction, and that process is called reductive amination, and it's a nice way of making amines. And so again, in sort of very broad view from 30,000 feet abstraction, if we have some sort of carbonyl compound and some amine, some RNH2 amine, and we envision going ahead and again treating with the right hydride under the right conditions, you can both form an imine and reduce the imine often by way of the aminium ion all in the same pot. The reagent that's often used to achieve this transformation is sodium cyanoborohydride, NABH3CN. Now, we've already seen various hydride reducing agents, you've seen lithium aluminum hydride, you've seen sodium borohydride, you've I believe seen lithium tri-terbutoxy borohydride, and they all have slightly different properties. Lithium aluminum hydride has that aluminum hydrogen bond that's very polarized, you end up with a very potent hydride source. Boron is less electropositive, it's more electronegative than aluminum, less electropositive, the bond isn't as polarized, it's a milder hydride source. So sodium cyanoborohydride, here's the cyanoborohydride anion, is in many ways like sodium borohydride, but less so. The cyanobroup is electron withdrawing, it's pulling electron density away. So sodium cyanoborohydride is even less willing to donate a hydride, and that's good because it's not a good enough reducing agent to reduce a ketone, but under the reductive amination conditions, you form as an intermediate, you form an aminium ion, and the aminium ion intermediate is more electrophilic than a ketone, and so sodium cyanoborohydride can add hydride to the aminium ion in the course of the reaction. And so often in one pot, you can mix a ketone and an amine or a ketone and an ammonia and sodium cyanoborohydride, sometimes with a little bit of a mild acid like acetic acid, in order to go ahead and form an amine. So if we take benzaldehyde, and we treat it with ammonia and sodium cyanoborohydride, NABH3CN, you get benzalamine, you form the imine or rather the aminium ion forms transiently, and the cyanoborohydride adds hydride to that and reduces it to the amine. You can do the same thing with a ketone or an aldehyde, so I'll just give you one more example. If you take cyclohexanone and you take, I don't know, let's take neopentalamine as an example, tertbutylamine, not neopentalamine, tertbutylamine as an example, and subject it to the same conditions, so I'll just write ditto over here. Now you can form a secondary amine like so. Chemists, as I've emphasized all along, like to be able to build molecules. It's useful to be able to take simple stuff and make it into more complex molecules, yes, including cocaine, which one can synthesize chemically and morphine. The nitrogen atom is a beautiful lynchpin for synthesis because the nitrogen atom is nucleophilic and so it can act as a nucleophile in an SN2 displacement reaction. So it seems like it would make sense that a useful way to go ahead and build up complexity in a controlled fashion would be to alkylate that nitrogen, but it's not so simple. Usually the product of the reaction, which is also an amine or really an ammonium salt and equilibrium with an amine, usually the product of the reaction is even more nucleophilic. So if I take benzolamine and I treat it with methyl iodide, CH3I, even if I use one equivalent, you'd say, well, that should be an easy reaction. I should just get the monomethylated product. And the problem is as the monomethylated product forms by an SN2 displacement reaction, protons come on, protons go off as the reaction is proceeding. You have amine present and so now you have methylamine. So you also end up getting the dialkylated and trialkylated products as a mixture. The trialkylated is the benzol trimethylammonium ion, which is actually used as a germicide in things like eye care products. So the overall result is you get a mixture of products and so if you say, oh, I want to be smart, I know how to make methylbenzylamine, all I do would be to treat my methylbenzylamine with methyl iodide and then do a basic workup. The problem is you generally, and this isn't always true, but you generally cannot get a monoalkylated product in a controlled fashion. So the big problem is once the SN2 alkylation has occurred, the amino group, well it's protonated but protons come on and off under the reaction conditions, the amino group is still nucleophilic and still available to undergo alkylation. In fact, it's even a little more nucleophilic. So imagine for a moment that I wanted to go ahead and do an SN2 reaction. Imagine for a moment that I had hexal bromide and I wanted to treat it with ammonia and I've already said on the previous blackboard, I get a mixture of products. The solution that chemists have developed is to take away the nucleophilicity of the amine after it's done the alkylation to make it so that it's no longer nucleophilic. And the solution to this is called the Gabriel synthesis of primary amines and it's to use an ammonia surrogate. The ammonia surrogate is thalamid, P-H-T-H-A-L-I-M-I-D-E. It's an imid and imid is like an amid with two carbonyls on the nitrogen. It's the nitrogen analog of an anhydride. The proton having two carbonyls next to it is extra acidic and so a base like sodium hydroxide can pull it off. Your textbook lists the pK about 10. Other sources list the pK about 8.  The anion is nucleophilic but it's nucleophilic in a controlled fashion. So now if you add your alkyl halide that can participate in an SN2 reaction, if you add your hexal bromide, now you go ahead, it alkylates and then what you can do, what you can do now is in another step treat with strong base or strong acid. So we'll go and treat this with sodium hydroxide. You can also use hydrazine but we can use sodium hydroxide, water and heat. And that goes ahead and it makes your amine and it also makes as the byproduct it hydrolyzes the imid and there are other sorts of synthesis using surrogates, using protected groups in order to allow the synthesis of secondary amines. There's a Fukuyama amine synthesis which I won't show you. All right, I think this is a good stopping point. We will pick up with more chemistry of amines next time.


Since the invention of the first electronic communication systems in the 1830s, the world has been changing. Information and communication technologies, ICTs, are evolving at an ever faster pace, reshaping the world around us. In 1998, the United Nations proposed a new kind of global dialogue on the impact of technology, called the World Summit on the Information Society, or WISIS for short. This meeting was the first UN summit-level discussion open to all. We wanted to hear from everyone, everywhere. Because if technology is really going to change our lives for the better, no one can be left out of the conversation. Together, the world agreed on a blueprint to guide the equitable access and ongoing development of ICTs. In the decades since, these principles have shaped global efforts to harness technology to drive development and foster innovation. Today, the WISIS process is an ongoing, inclusive global dialogue, aimed at ensuring we fully leverage the power of ICTs to meet the sustainable development goals. And every year, the WISIS Forum gives the global community the chance to take stock of achievements and remaining gaps. WISIS remains the most open, inclusive and accessible global platform on the way technology is changing and enriching all of our lives. ICTs are key to achieving truly global, sustainable development. Let's ensure no one is left behind.


Welcome back with us, folks. Tonight we are talking about relative strength. The market has been going down about like this or I should say a little more like that. It's been tough. It's been a red beginning of 2022. However, we will find and the idea is to find the ones that are still strong within this dip. When the market catches up, when the market gets a grip, the idea is to be in and to be able to trade it as the market moves back up. However, well, you can short the market, but what I want to show you here is who's strong while the rest is sinking. And we talked about last week while the market was dropping, we talked about UPS. And if you see from Wednesday, basically it's been pretty straight, trading pretty straight. The rest of the market was really, like I said, dipping that way while this one was still managing to get some strength. And this is what we need to focus on. The rest is sinking and this one is holding. Usually in, you know, this is end of day on Thursday when everything was falling apart. You see a reaction. Outdoors will trade the whole thing to the downside. The tick to the downside is increasing on all tickers. However, if you look at the rest of the week, Wednesday, let's go on Thursday directly. It was upgraded. It's been kind of finding a bottom here. It's consolidating at a bottom. And if you look at the market, look at what it did. Here there's a level higher low. And then we find the same level here. So basically, and this is after hours. And we reopen and this is when we had an upgrade on UPS. And it still finds the same level. So looking at this chart here, I mean, forget about that. That side of the chart for now. When you look at all this here and get an iron higher low on this, on these two guys here. And then bottom, bottom is all grabbing. And we see here, it just won't cross pretty much a little lower than that. But buyers found whenever they were here and here, they're pushing it and trying and trying and see how all of this is getting tighter and tighter. Now I'm talking about this because it didn't care about the fact the market was going that way, right? And we're not talking about an unknown ticker. I'm not saying that it's the biggest ticker in the crowd, but it should trade according to the rest of the market because market sentiment usually allows people to say, okay, if the market is stinking, market economy is not doing so well, so UPS should be in the same kind of group. So what I'm showing you here is strength in order to be able to realize what's going to happen whenever the market decides to go in a different direction. And we all saw it lost support here pretty much just like the rest of the market. This comes to exactly the point I wanted to show you. Is this when we open on Friday, it's just very tight, tightly consolidating at a level very close to this one. See here at the on the left side. Basically this was low of this week. And then we're pretty much trading at that low. Yes, there was this little wick here, little wick which is grabbing a lot of stop orders. Make sure that then they start moving it up. Now, let me zoom in on this for you here because this is where it gets important, right? It's extremely tight. The rest of the market doesn't want to follow and then this one starts to move to the upside. This is the strength I'm talking about. The rest is falling and this one is moving to the upside. Can you imagine when the market decides to move to the upside with this is going to happen with. So we took a small position. I'll zoom out a little bit. We took because I want to show you something here that we previously talked about. But the idea was we saw this bottom here very almost very close to the open. And we decided to go to 10 to 10 for next week. We're at Friday. Obviously, theta is going to go against us if we hold forever until expiration because, you know, it needs to be in the money in order to have some value in it. But it was cheap. It was $41.41. The idea is we want to cross this eventually. When we start crossing, there's no resistance or very hardly any to the upside. So it is to eventually get in the money. However, we need to start from the bottom here and at least get to the first resistance. What did I tell you about, right? This was resistance at the open. And this again, it found. Sorry, I'm explaining myself wrong here. This was support. I'm talking about resistance because we're buying the bottom, but this used to be support. This used to be support and this used to be support from the open. So we can really think that either this area where they found buyers or at least the old support where everyone started buying would be a line of interest. Let me get out here and show you something. And this is all to show you something about a target. You are entering this play at this level at the bottom. And you know, you can at least get to some sort of. A rise. You know, we're in the two two oh one area. We're going to at least two oh four fish, right? Because this is very close to two oh four. And the idea is at least if we were to enter this, it would be great. Once we enter this next line is up there. And then it's really going to move to the outside. So took to then to 10 for the next week paid 41 cents. We sold a little well half the position at a little over 100%. I believe it was in the 90 ish section 90 ish area, maybe a little over that. But look at what happened. And this is the important part. The where did it stop? And I'll show you exactly. This is where it stopped, right? It stopped where I told you we are here, here, here used to be support. And now what? Now it's resistance been saying this for quite a few videos. I guess this lost support. It's breaking under and it's testing it again. All of this was strength where while the market was tanking and we only took a bottom. And drove it to the. And it's the same bottom and drove it to the old support. And now it's resistance. So I hope you guys are learning something or getting some ideas about what can be done. This market tanking while we have a strong ticker will always be a good suggestion to keep an eye on and maybe trade it just like we showed you. Support resistance, simple. Thanks for watching, folks.


Let's talk about five sins of the tongue that too many Christians commit, many without even realizing it. Whenever we talk about sin, we always picture what we would deem as the bigger sins and often we overlook what others would call smaller sins. So I wanna show you from scripture these five different sins of the tongue. And as you begin to see these, I pray you ask the Holy Spirit to bring correction, to bring conviction. This will save your reputation. This will save you a lot of time where God will not have to bring correction if you repent in these areas. This will help you in terms of your joy, in terms of your peace, in terms of your clarity. Because what you say affects the way you think and what you think affects what you say. It's a cycle that you get caught in if you're not careful. And so I want to teach you something that's going to help you walk in peace, walk in favor, walk without having to be under God's correction, walk in a good reputation. I pray it challenges you if it's an area that you need to correct. But let's talk about these now. The five sins of the tongue, too many Christians commit. Proverbs 18, 21 says, the tongue can bring death or life. Those who love to talk will reap the consequences. Now here, many have applied a superstitious reading of this particular scripture to mean that whatever I say will instantaneously materialize in some magic way. That's not exactly what the scripture is describing here. The scripture is saying here that there is power in your words to affect your life. What you say can affect what others around you think. What you say can influence what you think. What you say can harm your reputation. What you say can invite God's correction and even judgment. And this is why we have to be careful about what we say, because what we say can bring encouragement or discouragement. What we say can bring clarity or confusion, unity or division. James chapter one, verse 26, if you claim to be religious, but don't control your tongue, you are fooling yourself and your religion is worthless. James three, beginning at verse three, we can make a large horse go wherever it wants by means of a small bit in its mouth. And a small rudder makes a huge ship turn wherever the pilot chooses to go. Even though the winds are strong in the same way, the tongue is a small thing that makes grand speeches, but a tiny spark can set a great forest on fire. And among all parts of the body, the tongue is a flame of fire. It is a whole world of wickedness corrupting your entire body.  People contain all kinds of animals, birds, reptiles and fish, but no one contain the tongue. It is restless and evil, full of deadly poison. Sometimes it praises our Lord and father and sometimes it curses those or wishes harm upon those who have been made in the image of God. And so blessing and cursing, come pouring out of the same mouth. Surely my brothers and sisters, this is not right. Number one, complaint. Now this is not what you'd expect in terms of a sin of the tongue, because sometimes we don't realize that complaint actually proceeds from the heart. Now the next point I'm going to make when I talk about number two, that's gonna be a very obvious point. And when I say it, you're gonna immediately agree that that is definitely a sin. Probably not one talked often enough about, but here at this number one point that I'm making, many people wouldn't expect to see complaint on this list. Philippians two, verses 12 to 15 say this, dear friends, you always followed my instructions when I was with you. And now that I am away, it is even more important, work hard to show the results of your salvation, obeying God with deep reverence and fear for God is working in you, giving you the desire and the power to do what pleases him. Do everything without complaining and arguing so no one can criticize you. Live clean innocent lives as children of God, shining like bright lights in a world full of crooked and perverse people. So here the scripture tells us to do everything without complaining and arguing. And in so doing, no one can criticize you. Here we see that our reputations are spared when we don't complain. Let me just put it to you bluntly. Complainers are difficult to be around. If you find that people find it difficult to be around you, consider what comes out of your mouth. Consider the words that you speak. Is it possible that people hesitate to bring you around because you're constantly speaking negative things and they don't wanna be around that? I'm not saying that's the only thing that it could be, but at least you have to evaluate this point.  People look and they see that it's not very Christ-like, live clean innocent lives as children of God, shining like bright lights in a world full of crooked and perverse people. So obviously the scripture is not just describing the fact that we shouldn't complain, but it throws in that instruction among others. And here we see that by refusing to be complainers, we become shining bright lights for others to see. It's part of our testimony. Complaint reveals lack of gratitude. Let me say this again. Complaint reveals lack of gratitude. Lack of gratitude reveals a heart that is not focused on Jesus. I wanna say that again, and I want you to think about what's being said. Complaint reveals lack of gratitude. A lack of gratitude reveals a heart that is not focused on Jesus. How can you complain? How can you be unsatisfied? How can you be bothered by your circumstance when you're focused on Jesus? Hebrews 13.5 says, let your conversation be without covetousness and be content with such things as you have, for he hath said, I will never leave thee nor forsake thee. So here the scripture is making it very clear that the very presence of God is the source of contentment for our lives. And so if I'm complaining, it's because I'm not content. And if I'm not content, it's because I'm not centered on Christ. When I'm centered on Christ, I'm fulfilled. And when I'm fulfilled, I don't complain. Now I'm not saying that we can't acknowledge things that are wrong, and I'm not saying that we can't acknowledge things that need to be corrected. Of course, it's healthy to do a realistic evaluation of your life and circumstance. And those of you in ministry, those of you who run businesses, those of you who help to facilitate things and those of you who are trying to build a strong family, your leaders, your people who are trying to build, you're trying to accomplish, you're trying to do the will of God, of course you're going to have to point out flaws from time to time. Of course you're going to have to point out things that are missing from time to time. I'm not saying you don't do that.  You complain about others. You complain about what you don't have. You complain about what is happening. You complain about what isn't happening. And this isn't the way that the believer ought to live. When you hear believers say things like God never answers my prayers or it's been decades and I still don't see that God's given me breakthrough. Usually it's because they're so focused on the negative that they can't see what God is doing. They're so focused on what God isn't doing that they can't be thankful for what he is doing. And so that complaint is produced. They're constantly spewing that out of their mouths saying things like, well, God isn't ever there for me. God is never there for me. God doesn't answer my prayers. God is ignoring me. I'm not blessed and everything always goes wrong in my life and they live like this and they feel justified in their complaint, not realizing that that is coming from a heart that is corrupted by a lack of focus on Jesus. Now again, I wanna be clear. I'm not saying that you should never acknowledge that which needs correction or improvement. Of course you should. You ought to be realistic but make sure that the heart posture isn't one that is dissatisfied because it is not focused on Jesus. Number two, and as I said, this one's gonna be very obvious but I wanna point this out here. What I'm about to say will seem very obvious and the moment I say it, you're gonna go, of course. And in fact, if you read the title or maybe heard my introduction, you probably knew that this one was going to come up. But this often comes up in ways in the life of the believer that they're not even aware of. So don't just dismiss this point that I'm about to make and say, okay, yeah, I know what that one is. So I'm gonna check that off, dismiss it or accept it, repent of it or think of it in a very clear way. But often this appears in very subtle ways and that is number two, lying. Now again, I know that would seem obvious but deception or deceptive talk or deceptive communication often comes about in ways that we may not even intend. I'm not trying to scare you, I am trying to prepare you to live in a way that avoids this kind of sin. Colossians three, I'll read verses eight and onward but now is the time to get rid of anger, rage, malicious behavior, slander and dirty language. We'll come back to this portion of scripture in a moment, there's a lot there.  Put on your new nature and be renewed as you learn to know your creator and become like him. So here we understand that because we've been made new we can now be free from deceptive talk because we are new creations we don't have to rely upon lying anymore. Some people that's a way of life for them that's how they get by. Some people struggle with compulsive lying. In other words, they just lie because they don't see any immediate benefit other than the fact that they enjoy lying or that they have this compulsion to lie. But again, lying is not just this very obvious blatant sin that we commit. We all know you shouldn't deceive. We all know that you shouldn't say things that are blatantly obviously false. We all know that you shouldn't give bad information in an attempt to save face or avoid consequences. But think about the fact that there are also what we would call half truths. Sometimes we deceive not just in what we say but in what we don't say. Sometimes we manipulate people not just by the information that we give them but by the information that we don't give them. What's more, we also exaggerate or make understatements. Exaggerations and understatements are a form of lying. Now, if you're talking about poetic hyperbole or exaggeration for the sake of communicating a very specific point, it's very obvious that you're making that exaggeration that's different. Again, poetic hyperbole is not what I'm talking about here. I'm talking about exaggerating to boost your ego, exaggerating to be looked at in a certain way, exaggerating to be perceived in a certain light, exaggerating to gain a certain status, exaggerating to gain favor with a certain person or an understatement, downplaying something to manipulate the situation or the person that you were downplaying that fact too. I see it all the time on social media. People exaggerate, preachers exaggerate. My goodness, I can't tell you how many times I've scrolled through social media to look at a picture of a couple hundred people and the caption reads, 5,000 people gathered, 10,000 people gathered and I'm looking at that going, that looks like maybe three or 400. Or they'll say things like, look at how many book sales I've had or look at how many followers I've amassed or look at how many people I've reached and there are exaggerations sometimes to these statistics and that's not just Christian leaders. It's also the body of Christ at large who makes exaggerations or they try to create this image in life that maybe gives the wrong perception. I'm not saying that you have to put everything online or everyone has to know everything about you. I'm saying that sometimes the exaggerations that we put forth are done so intentionally so that we can communicate a certain thing that isn't necessarily true. And that's not a blatant lie. It's not outright saying something that isn't a fact all the time but that exaggeration serves a purpose of manipulation. Exaggeration can often serve the purpose of manipulation and so can understatements. Again, not just in the information I give but in the information I don't give. Now this next one can really harm your reputation. So we've talked about complaining. Complaining is not just speaking negative from time to time. I'm talking about a disposition, a posture of the heart that comes about as a result of not being focused on Jesus or satisfied in him. And number two is lying and we also talked about the fact that it's not just the blatant communication of bad information but it's also the withholding of information for the sake of manipulation as well as exaggerations and understatements and have truths if that could even be considered a thing. Then number three, and as I said, this one really can damage your reputation if you're not careful. And I plead with you as a believer to consider your Christian testimony. I'm about to say it right now. Consider your Christian testimony. Consider how what you do reflects upon Christ. Consider how it affects those closest to you. Consider how your children are watching you. Consider how the people you're discipling are watching you. Consider how your coworkers are watching you. This is number three, and again, this will damage your reputation if you participate in this lie. Number three is in this sin. Number three is gossip.  We're gonna cover that in the next point. I'm gonna tap into that a little bit more because the next point I'm going to make is actually a little bit more, I think, damaging. But this is more than just communicating a lie. This is just sharing information that isn't yours to share. It's sharing information that you are entrusted with. It's sharing information that you have nothing to do with. Proverbs 2019, a gossip goes around telling secrets. So don't hang around with chatterers here. Proverbs defines for us who the gossip is. And gossip, by the way, isn't just making up lies about someone. Gossip is communicating information that you are entrusted with, or information that someone else was entrusted with but gave to you, and spreading that around. That is wickedness. That is immaturity. Now, you can say things like, well, I'm really close to them, so I should be able to tell them. Or, well, when they tell me, they know they're telling them. That's a lie. In fact, when people come to me for counseling and ministry, one of the first things that sometimes they ask is, is this information safe with you? Is anybody else going to know this? And I have an agreement with my wife, Jessica, that as long as it doesn't involve me or her and I, that if that individual is just communicating information about their life that they need help for with their situation, then I'm not even gonna communicate that to Jessica. And she respects it. And I tell her the same thing. I say, my dear, when somebody entrusts you with information and insecurity, something they're struggling with, something they're dealing with internally, you do not tell me this. Unless, again, it has to do with you or our marriage or our daughter, you keep that between you and them and I will respect that. And often we'll see gossip go not from friend to friend, but from the friend to the friend and to the spouse. That's gossip. It's not yours to share. Now, people may say, well, we are one, so they know if they're telling me, they're telling the other. Well, then you have to communicate that to the person as you're talking to them. Let them know, hey, I have an agreement with my spouse. We tell each other everything no matter what it is. So if you communicate this with me, you're communicating with my spouse. At least let them know that if that's what the arrangement is in your marriage. But for the sake of what I do, sometimes I have to be protective of people's insecurities and things they've dealt with in their past and things that they're holding real close that maybe they're ashamed of. I'm not going to communicate that with anybody unless of course they committed some sort of crime then I gotta go tell the authorities. But barring that, that's not something I share at my spouse and Jess knows she doesn't share other people's information with me. Nor do I share it with my close friends. We have this agreement with, we call it the vault. Like it's something that here we have on the team. And so my wife and I understand it. I have this with my brother, Steve and a few other individuals here that if they want information or what happened with that conversation. Again, as long as it has nothing to do with them and it's not going to affect them and the individual didn't give me that information or didn't bar me from sharing that information that's different. But I'll say that's in the vault, I can't communicate that. That helps your reputation. But when you're the type of person who will take something and you say, well I only told people I could trust, that's deception. Let me just tell you bluntly that's deception. That is wrong. That's immature and it's a betrayal of the trust of the individual who gave you that information. Well, they should know I'm very close to them. Well, then you tell them that you're going to tell them before they tell you because it's not your information to give and people do it all the time in the church. Well, I only told so and so because I knew they wouldn't tell anyone. Well, it wasn't your information to give and it was actually a form of lying if you put up a front as if you weren't going to share that information. Now again, if we're talking about crimes and sins that need to be confronted, that's very different. I'm talking about things that people communicate in vulnerability to you. You have to vault that. Be a vault. I want you to type that in the comment section. Be a vault. Be a vault. Proverbs 16, 28 says, a troublemaker plants seeds of strife, gossip separates the best of friends.  How can I truly help people who can't be vulnerable because they're afraid of their private information going all over the place? And it's wrong. That mindset of I can tell just a few people because that is immature. It's childish and it needs to be dealt with in your life if that's something you're allowing. Be a vault. And so again, if in your marriage you think that that information needs to be shared, then you need to communicate that with the people communicating with you saying, hey, whatever you tell me, I'm gonna tell my spouse. And that's fair. But it's not just yours to front and say, well, I'm gonna pretend as if I'm not telling anyone and then go and do that. That's ungodly. Number four, and this one, by the way, proceeds from ego and jealousy and bitterness and self-righteousness. Number four comes from self-righteousness. Number four comes from the ego. Number four comes from jealousy. And this right here is even worse than gossip. Holy spirit, I pray you convict us in Jesus' name. Number four is slander. Now Colossians three, eight through 10 says, but now is the time to get rid of anger. We just read it. Malicious behavior, slander and dirty language. And we covered, of course, the rest of this portion of scripture. Slander is speaking with the intent to harm someone's reputation. Slander is speaking with the intent of turning people away from certain ministries, churches and individuals. Slander is the attempt to get people to perceive people as negatively as you do. Now let me tell you something. I'm gonna clue you in to a little secret that probably people who are in media wouldn't like me sharing. When you study media, there's this concept that comes up called controlling the narrative. News anchors control the narrative. Newspapers control the narrative. Radio hosts try to control the narrative, especially in politics, there's this implementation of tactics to try to do what's called quote controlling the narrative. And by that I mean they take all of the information, they take all of the facts, they take all of the stories, they take all of the video clips, they take everything and they try to shape this narrative and try to get you to view that person in the negative light that they view them. What's actually happening is they're exposing their own heart. They're exposing their own ignorance. They're exposing their own bitterness. They're exposing their own pettiness and immaturity. Why? Because they're not satisfied until people begin to believe what they believe about that individual. It's not just good enough that they believe that individual is to be seen in a negative light, but they have to now go and get everyone else to see them in that negative light. And if people don't see them in that negative light, they're offended by that personally. They're bothered by that because they didn't have as much control and influence as they imagined that they did. And so we see this in churches. We see this in families. We see this in the media. We see this on social media. We see it all over the internet where people seek to control the narrative. You know, you can make anyone look bad by what you show, by what you don't show. How many times have you seen someone present a clip and say, well, there it is in their own words? Well, if you're introducing the clip, setting up a narrative, a perspective, trying to get them to see it in a certain light before the clip is even shown, and then commenting after the clip is shown, and you're saying, well, look back there. This is how I perceive it. This is how you have to see it now. Well, of course, you're gonna be able to get them to see it in a certain light. That right there is manipulation. That right there is wickedness. That right there is demonic. And you see people do this against men and women of God all around the world. You see them try to tear down their reputations through crafty narrative control, through taking certain clips and taking certain stories and presenting it in a certain angle. And then they do what's called emotional pleading, leading questions. In other words, they ask you questions about the person's motives. They try to assess and analyze and theorize about what the person was thinking or not thinking, or what the person's intentions were, attitudes were. It is witchcraft, and it is a sign of self-righteousness. People of God, we have to be aware of this. Not only should we not participate in slander, but we should also reject slander as a whole. Don't watch it. Don't converse with people who talk like that. And remember to always give the benefit of the doubt. Keep a level head, assess the information for yourself, and realize that anyone could be painted in a bad light with enough crafting of the narrative. And that right there is slander. Don't listen to it. Don't participate in it. Because again, it happens in families. Maybe you have some family members who are like that. They take your every action or inaction. They take every story and twist it. They take every occurrence or instance and put it into a certain framing. They try to move it and describe it in a certain way. They set it up when they go talk about you.  You know how so-and-so is always complaining? Or you know how so-and-so is very negative? Or you know how so-and-so is very given to anger? And they just set it up in a certain way. And it's witchcraft. It's witchcrafting. It's narrative control. It's mind control. And it is manipulative. And often they'll come across like they're trying to be protective of you. Often they'll come across like they're just trying to speak the truth. Like they just care about people. Oh, my heart goes out. Oh, I just care too much. Oh, I just want the truth to go forward. Manipulation. And if you can see past it with the discernment of the Holy Spirit, you should call it out for what it is. Have no part in slander. And if I'm describing you, you need to repent. Slander is satanic. So number one, complaint. Number two is lying. Number three, gossip. Number four, slander. Number five, Jesus himself addressed this one. Jesus himself addressed this one. Number five, Luke 6, 27 to 28. But to you who are listening, I say, love your enemies.   Pray for those who mistreat you.  No, when he's talking about cursing, he's talking about insults. He's talking about wishing harm upon someone.  To curse another person, to wish harm upon them. In fact, as you study this in particular context, not necessarily in every context of scripture, but when curses are being described, I think it's actually even in the portion of scripture that we read in the book of James, I believe it was. If I'm remembering that correctly, that in that context, cursing was being described as to wish that the people were cut off from God, to hope for their damnation, to wish that they went to hell. That was a form of cursing. And so often, we speak in anger, insults. We speak in anger, harm upon people. We speak in anger, hoping that bad things happen. That is cursing, insulting them, criticizing them, name calling, tearing them down, bringing up their past, bringing up their flaws, bringing up all the ways that they failed you. We're tearing them down. We're using our words to bring harm upon them. That is not the believer's way. That is not Christ's way.  When someone criticizes you, you return that with blessing. Now it's not always easy to do easier said than done. I myself am tempted sometimes to retaliate when people come against me. But you know, you leave it to Jesus. You leave it to the Lord and you bless them and you pray for them and you keep your heart pure. Let God deal with others. Maybe there's someone in your family who's cursing. Maybe there's someone in your local church. Maybe there's someone at work, maybe at school. Maybe there's someone online who you've been friends with for maybe 10 years. You haven't talked in a long time, but they're always putting these subtle little jabs that you, in the comment section, whenever you post about your family or an outing or anything good happening in your life, bless them and guard your heart. Father, I pray you help us to do it. We repent of all these things. I want you to say that right now out loud. Say, Lord, Jesus, I repent. Forgive me, Lord. We ask you to do it in the name of Jesus. We honor, we bless you. And I want you to say it because you believe it. In fact, type it in the comment section, type amen. If you enjoyed this message and you think more believers need to hear it, leave a like on this video right now that helps to spread it even further. Let's you and I stay connected. Make sure you subscribe to my channel so that you can continue to receive my teachings on the Holy Spirit prayer and spiritual warfare and other topics like this. Now, I need your help with something. Maybe you've been watching this for a while. You've been watching our channel. You've been receiving from the ministry in some way and you are being blessed by the Lord. You've been maybe saved, healed, delivered in power through God's work through this ministry. I need your help with something. Our ministry is growing exponentially. And it's funny because I say this constantly, but just when I think the growth is plateauing, we see another growth spurt. But along with this comes growing pains. And growing pains are good because growing pains mean you are growing. We as a ministry are having now to put out more content in terms where it goes and how many it reaches. We're having to put on larger and larger events. The demand on this ministry is growing. People are being affected in a positive way. They're coming to Jesus. They're being set free from addictions and bondages. They're being healed of sickness and disease. They're being empowered to walk in their callings. And now I need your help. Will you help me by partnering with this ministry? Join this movement. And it is a movement. Only God can do this. The favor that's on this movement. The excellence that's on this movement. The growth that this movement is experiencing. Only Jesus could do it. And to him and him alone belongs all the praise, the glory and the honor. So I'm asking for your help. Will you help your brother in Christ? Will you help send us to the nations? The nations are calling. And we wanna say yes. The expenses are growing along with the impact of the ministry. So will you do your part by getting involved right now? Become a monthly supporter of the ministry by going to davidhernanisministries.com slash partner. Think of all the things that we spend monthly on. When I'm asking you to spend monthly on a ministry. Go sign up today. Open the webpage, davidhernanisministries.com slash partner and say, Holy Spirit, what would you like me to give? You can also give a single gift by going to davidhernanisministries.com slash donate. We accept currencies of all kinds from all different countries, including cryptocurrency for those of you who've asked. Try the website first, davidhernanisministries.com slash partner or slash donate for a single gift. And if those don't work for you from your region, you can give to the social media platforms, but do go and do something today. Don't say somebody else. Don't say some other time. Just open one of those web pages and ask the Holy Spirit what you want to do. I love you. I appreciate you. And I pray for you. Until next time, remember, nothing is impossible with God.


My name is Jane Roussak. I am the EGU Events Coordinator and I am based in Munich for the last year and a half, but previously lived in Canada for 17 years. This will be my first EGU General Assembly. Yes, I'll be attending in person and also visiting Vienna for the first time. I joined the Union Office at the beginning of the year to help with the planning of the annual EGU General Assembly. So I'm acting as a liaison with Copernicus, who is our third party conference planner, and I'm also assisting the program committee as well as the program committee chair with Planning Matters. So the biggest challenge has been organizing a large-scale event in response to the ongoing pandemic. We wanted to avoid a fully virtual event for the third year in a row, as majority of our community expressed interest in a in-person meeting. So listening to our community's needs while ensuring their comfort and safety is of the utmost importance to us, but for us this also means we have to closely monitor and adapt to the ever-changing COVID-19 regulations. So the biggest goal is taking the next step in our journey towards a fully hybrid meeting. So for us this is really exciting to be able to provide both virtual and on-site attendance options. So it means that our community members can choose the participation style that works for them. For me, I'm super excited to see it all come to life. The realization of all the puzzle pieces and hard work, not only from the EGU staff and Copernicus, but also all of our scientific divisions and many volunteers that make this possible. I look forward to experiencing the feeling of community that our General Assemblies are known for, and of course to connect with Geoscience lovers like myself. I encourage our participants to take advantage of the online display materials to get a deep interaction around the science. So the uploaded materials can be commented on through the conference platform during a two-month period between May 1 and June 30. We look forward to welcoming participants both in-person and virtually at this year's EGU General Assembly.