Okay, hello, and welcome back to the channel. Hope you had a great weekend and not too much in the way of major Market-moving information coming out this weekend more so a look ahead for the week because of course we've got US CPI coming out on Tuesday, it's really the highlight of the week We've also got US retail sales housing and starts permits weekly jobless claims And we've got also major UK economic data throughout the week jobs date on Tuesday CPI Wednesday and retail sales on Friday as well So before I begin if you're new to the channel, if you like what you hear don't forget to like and subscribe to the video But let's dive straight in and talk about US CPI and this is what we can see here the year-in-year figure on My screen right now and although US inflation you can see here is being quite clearly Trending lower since we peaked in the summer of last year You can see we've gone from 9.1 all the way down to 6.5 percent economists have forecasted in January The decline will likely have moderated somewhat Owning to persistent price pressures particularly in housing and an uptick in the prices of energy and also used cars So let's just dive into that a bit more details So in terms of expectation a year-in-year is expected to have declined but again at a more moderate pace So instead of dropping like we saw last time 7.1 down to 6.5 is expected on a median consensus basis on the street to drop down on the year-in-year reading to 6.2 percent That would represent though the slowest rate since October 2021 but the smallest decrease in the annual rate since September going back to here Higher petrol prices is expected to have boosted the the top headline rate Looking over at the core figure. So that's what we're looking at here You can see we peaked up in the last 12 months readings going back to September last year at 6.6 last time out We were down at 5.7 This core reading of course is what strips out things like volatile components like food and energy It's expected to slow to an annual rate of five point four percent down from five point seven High rents will have prevented a bigger drop though in core inflation as according to Barclays They're particularly putting a lot of emphasis on higher prices of used cars And that's been something that's been quite common amongst the bank research. I've read this weekend The jump in auto sales saw dealers raise their profit margins with car auction prices jumping around two and a half percent According to Mannheim data and given the high weighting of used Vehicles within the basket of goods and services to calculate consumer price inflation This could add around point one five percentage points to the month-on-month month rate on its own Irrespective of everything else. So yeah, definitely keeping an eye on this one of the key measures Of course of the week and at the moment as far as the market is priced looking at federal funds rate futures still around 91% or so looking for a 25 basis point rate hike Following the downshift that we've seen from the Fed more recently the next rate hike though Not coming for some time not until the 22nd of March Also from the US though, we do get retail sales. You can see here We've had two negative prints back to back and the last month the worst of the bunch that we've seen in the last 12 readings one of the first things that the Dutch bank ING their analysts are noting is the weather is going to be particularly Prevalent for this particular data point will get on Wednesday The reason why is that January activity data generally they say is going to be strong throughout the contrast They say between the weather in mid late December where it was incredibly cold versus a very mild January Couldn't be any more different essentially and that means that they'll be delayed consumption plus better weather Meaning more people are out and about which likely means then the likelihood it will lift January spending and we could see this more evident in this week's number We already know that auto sales are very strong I just mentioned that and that will likely lift the retail sales Quite a substantial amount anyway on its own in terms of the street consensus looking for around a 2% positive reading So you can see here quite reversal from what we had last two months And in fact if it comes out just in line with expectations that will put us back up at a 12-month high going back to the high We had a January of 2022 the other things in the US to look out for this week as I said Thursday You get your regular weekly jobless claims data January housing starts building permits also coming out on the same day pivoting over to the UK CPI of course going to be the main feature of the three major releases UK annual inflation Is expected to have slowed to a four-month low of 10.2% you can see here that would mark from a decline of 10.5 so it would be pretty consistent But still at a quite high level certainly when comparison to when we were just looking at the US Analysts at invest tech they expect inflation to have subsided further in January because of lower fuel prices and more intense competition among retailers amid ongoing easing of supply chain disruptions and of course the Squeezed disposable income situation with the cost of living crisis still biting very much So at this present point in time, however, just flipping this over to the core rate Analysts expect that's when stripping out food and energy to have slowed to just 6.2 percent So just point one lower. So still hanging around up at this most elevated level that we've seen it Despite the more persistent slow decline that we're seeing so you can see here inflation really is Hanging tough a lot more than what we're seeing here in the core inflation reading in the US and the top headline rate Which has come down pretty rapidly the UK? Definitely not mirroring that to the same degree or at least the same aggressive nature Couple of things there in recent policy meetings this being the Bank of England officials have said they're now closely monitoring indicators of inflation persistence To judge whether or not further tightening is needed Remember they in the ECB didn't downshift like the Fed they stuck at the 50 basis point mark with that in mind It's the service sector components of the inflation basket So once again, the devil is in the detail and if you are really looking at these more closely Definitely go on the office of National Statistics website like you would in the US comparable the Bureau of Labor Statistics look at the CPI date of table and look at the Individual line-by-line items on the different categories to really identify this because service sector components of inflation basket They're typically less volatile, but tend to experience more persistent trends. So think of things like housing services recreational personal services things like that Rather than things like food for example That would see quite high jumps these other points are much more sticky and that's probably a reason why the Bank of England Gonna have to hang tough a little bit longer with the fact that more people are leaning on Kind of still rate rising at this point comparative to the Fed Even though the Bank of England might stop raising them cutting seems a distant far away future Comparative to what markets are expecting the second half of this year for rate cuts in the US Other things in the UK to account for we do have jobs data It's released on Tuesday be screwed nice for signs of easing labor market tightness Analysts at ING expect average earnings growth X bonus to accelerate to 6.5% in December from 6.4% in the previous month So again another quite key thing here to monitor in the UK at why inflation has been so sticky And then retail sales on Friday in the UK real-term spending has fallen in 12 of the last 14 months in the UK And it's unlikely that January was any exception And if so that would point to a modest fall in GDP through the first quarter as the main likelihood So that is it. I'm not gonna go any further than that. Hope it was useful Just encapsulating some of the key things to look out for so best of luck, and I will see you next time. Take care


Okay, so there's an exam next week and it's going to be on Wednesday during the regular class time. My office hours tomorrow have to be moved because I have to do these kind of make-up lectures with Sean tomorrow. And there's no group meeting for my group this week in case you were interested in showing. Thank you for your interest. I wanted to say something about this mechanism. I think it was Beth, Beth, who asked about this on yesterday during our discussion section. I looked up the mechanism for this O-silation in the presence of pyridine and they refer back to some earlier mechanistic papers. And I think the mechanism does involve, as somebody was, thank you for asking about that. Yeah, I didn't realize this, that even in the present, I mean the mechanistic studies were for DMAC, but from what I can see it looks very similar. These go through an en-silal intermediate. So the leaving group is not chloride in the catalyzed reactions, it's pyridine, which doesn't change our energy diagrams. But I learned something. I'd never known that those go through N-emidazoyl-silal intermediates before. I mean that's the more common conditions. Okay, let's go ahead and continue where we left off. You would never have known that. There's no way for you to have known that. Yeah, I wasn't asking you.  There's no conceivable way you could have known that without kinetic studies. No, no, you couldn't have known that. For this problem, well from now on, if I ask you about this mechanism in the presence of pyridine or emidazole, I want you to know that silatia with TBS groups goes through an en-silal species. But there's no way you could have known that ahead of time. Okay, so let me come back to this. We've been talking about carbocations and I want to talk about a little bit more about bonding and cyclopropanes. So we're continuing on with lecture six. And we left off talking about this idea that there's a lot of p-character. In order to adopt these very strained angles, if I look at a cyclopropane, there's a significant amount of p-character. This isn't sp3 hybridized. If it were sp3 hybridized, it would imply that there's 75% sp character in this bond. But there's more than 75% p-character. So as a result of this very weird hybridization in the ring strain, these bonds inside of a cyclopropane ring have more p-character. And are therefore more nucleophilic than your average run-of-the-mill carbon-carbon bond. As a consequence, if this carbon atom is using more p-character to make this bond, it has less p-character to make the bonds outside of the ring. So as a consequence of that, these bonds out here have less p-character than a normal CH bond. And as a consequence, they're less nucleophilic. So that's what's weird about the hybridization of that carbon atom. And we can put some numbers on that. For example, if I compare a cyclopropyl carbanion with just a regular run-of-the-mill alkyl carbanion, I'll try to put something in an unstrained ring here so we can compare. If I compare the basicity of this carbanion with the basicity of a carbanion on a cyclohexane ring, which is normal sp3, what you'll find is that this lone pair is 10 to the 5th less basic, right? The bonds on the outside of the ring have less p-character. These bonds or lone pairs are things that are sticking outside the ring have less p-character.  By a lot, 100,000 is a lot. Okay, so let's put some more numbers on this idea that bonding in cyclopropane can change nucleophilicity. And so I want to introduce you to a new term called cyclopropyl carbynil. That just means a carbon atom attached to a cyclopropane ring. And specifically, we're interested in carbocation that have cyclopropanes dangling off of them. And so let's see what happens in reactions that would make those kinds of carbocations. I want to consider SN1 reactions of some tosylates where tosylates is the leaving group. And if we just think about the relative rates here, I'll give you some relative rates relative to just ethyl tosylate, which you might expect as a pretty bad ionization reaction to give a primary carbocation. Of course, you can accelerate that by having a pi system next door. We have pi bonds next door. Why is this fast? It's fast because the pi system is donating into the anti-bonding orbital and helping to push out that leaving group. Or if you wanted to use the Hammond postulate and talk about carbocation stability, you could say, well, the carbocation is more stable and it looks like the transition state. But the bottom line is that pi systems next door, you should know that benzylic carbocations are stabilized and that benzylic leaving groups leave faster. And what I want to do is I want to compare this with a system where there are these strained bonds next door, not a pi system, but just a strained bond in that cyclopropane ring. So here's a bond that's sort of can potentially overlap in the right conformation with the anti-bonding orbital. This is 120,000 times faster than just a primary carbocation. All three of these are primary carbocations in theory. You get a sense that you may have thought that benzene rings and simple double bonds were all that for making alloy cations and benzene cations. But look at this, this is kind of pathetic looking in comparison. Cyclopropanes, this just gives you a sense for how awesome instability cyclopropyl carbinyl cations are. So let's go ahead and just draw out those cations. Here would be one cyclopropyl carbinyl cation. And I'll compare that to something that you might think is a great cation. I'll put a benzene ring on a carbocation. Then I'll add another benzene ring on a carbocation. And then I'll add a third benzene ring on the carbocation. This is called a trityl cation, triphenyl methyl. This is still more stable. This primary carbocation is still more stable than a trityl cation. Just to give you a sense for, yeah, yes, you can. I don't know, these are easier to attack. So there's other sites to attack that are kinetically not reversible whereas trityl cation addition is reversible. Okay, so cyclopropyl carbinyl cations are super duper stabilized. Look for reactions that make cyclopropyl carbinyl cations because those will be fast reactions. So I want to talk about the importance of the orientation of those orbitals. And I'm going to struggle here to try to draw out what kinds of orientations are good for stabilizing. So let me try to draw out a carbocation with an empty P orbital here. And the single best orientation for that cyclopropane ring would have each of these bonds sort of aligned so that they could both simultaneously donate into one lobe of the P orbital. That's the optimal conformation of a cyclopropyl carbinyl cation. Or sometimes you can tilt it so just one of them is perfectly aligned. That's also a good orientation. But in contrast, if you spin this around the wrong way, you'll get completely opposite effects. So here's my empty P orbital. There's my carbocation. If I spin this around so that this CH bond up here, maybe that's not a good three-dimensional drawing. So that this CH bond up here is aligned, that's lousy. That's a bad orientation for a cyclopropane ring. So you really want to have these, either one of these bonds ideally perfectly aligned, perfectly parallel to that empty P orbital. That's the ideal alignment. Let me, that should say, what was I, it looks like I was going to write something bad, but I meant to write bad, bad. If you want to write BA, never mind. If you want to write something else bad, it's bad. Okay, so let me compare two different systems. I want to look at a constrained system because I think maybe it'll be easier, maybe it'll be easier to see these effects. You can start off, I'm going to draw an adamantine ring system and you can start off by drawing a chair conformation. And I just want to be able to see exactly where that anti-bonding orbital is. There's an empty orbital there. And so why is it, what are the things that make this possible to ionize, this tosylate leaving group? There's an empty sigma star orbital here and there are things in this adamantle structure that are donating into that empty orbital. So specifically this axial bond over here and then one in back are aligned with that empty orbital and are overlapping in space with that empty orbital. They're donating electrons. So it's the donation from this sigma bond into this anti-periplanar, into the sigma star orbital of this anti-periplanar carbon oxygen bond. That's what makes it possible to ionize out this tosylate group. If you put, if you construct a compound that has a cyclopropane ring right here, that becomes way faster. It strains the bonds. It strains this bond so that this carbon atom has to use more p-character and when there's more p-character in this bond, when you have that cyclopropane ring there, it's 10 to the 9 faster. So a billion times faster with the cyclopropane there because that's a bond that's perfectly aligned. You're also straining this bond down here but that doesn't do you any good. It's not overlapping with the anti-bonding orbital. So let's take a look at a system that's not so well designed. Let me draw another atom, another adamantel system. I'll also start with a chair but I'm going to put the tosylate leaving group at a different position so I'll draw this with my axial bonds going down like this. And so now I have the capacity potentially to make a tertiary carbocation with that. Let's take a look at the bonds that are oriented with that anti-bonding orbital. Here's the anti-bonding orbital, it's on the backside of that tosylate leaving group, that's my sigma star orbital. And these bonds over here are aligned. Here's a bond that's aligned with that anti-bonding orbital. Back here is a bond that's aligned. Here's a bond that's aligned. They're anti-periplanar to that o-tosylate leaving group. If I make the mistake of putting the cyclopropane over here, that doesn't strain this bond. This is now like one of the bonds that's on the outside of the cyclopropane ring. This is now 1,000 times slower and I don't have room here but you would write with, I'll just write with cyclopropane, with CP. So with the cyclopropane, that slows it down. So you have to be careful how the cyclopropanes are oriented relative to that leaving group. It's not simply sufficient to be next to the leaving group. You have to worry about the orientation of those bonds in the strained ring. Okay, so I want to compare. Let me try to give you a resonance picture for what's going on and it's going to be very strange looking when we try to think about how do I draw this intermediate where there's cyclopropanes donating into an empty P orbital? Oh, you mean the shape, in other words, when I draw a carbocation, why don't I draw it like ChemDraw? But the actual shape of an empty P orbital, it looks like a sphere and I guess I never know how to draw this. It kind of bothers me to draw them that way.  That's the actual shape of a P orbital. It doesn't look anything whatsoever like this. Yeah, so whoever invented ChemDraw in the mid-1980s drew P orbitals like this and it's too bad they didn't draw them more like a half egg shape. This is just one empty P orbital. It's phased like this. I sometimes don't draw the phasing in just because. Yeah, so if I draw the extra parts of this empty sigma star orbital, it looks like this and if I include the phasing, it's hashed here, not hashed here so there's no interaction then hashed here again. So usually I just draw the big part. Yes, yeah, sometimes I'll draw like this but when I'm, I prefer to draw like that actually. Okay, so empty, so let's draw a resonance picture for a cyclopropyl carbynol cation. If I draw a cyclopropyl carbynol cation and I want to think about how do I represent this? There's really no perfect representation. If I really believe that this bond is donating into that empty P orbital like this, well why don't I draw a resonance depiction that looks like that? Here's what your resonance depiction will look like. It'll look like this. If I really believe this bond is donating into that then there ought to be pi character here in that cyclopropyl carbynol cation. There's another resonance structure I can draw is, well if I really believe that this carbon bond is donating into that empty P orbital, maybe I should think about this carbon bond as shifting over. Here's a different resonance structure I could draw where I lift this bond away from this dotted carbon here and then I leave a carbocation at that center. These are all valid resonance structures for a cyclopropyl carbynol cation. As hard as it is to think about three-dimensionally. What you find just to convince you that these resonance structures are valid ways to think about a cyclopropyl carbynol cation. If you make cyclopropyl carbynol cations, so if you take an amino methyl cyclopropane and you treat it with nitrous acid, you generate diazonium leaving groups, those leave in water, what you get is a distribution of products that contains this substitution product, you get this substitution product and you get this substitution product. You get all three of those substitution products. They're not all in equal ratios, that doesn't matter that much. You get the same distribution of products, you get the same products if you start with this leaving group on a cyclobutane ring. So you're sort of entering the same kind of carbocation if you start with the cyclobutane. Okay, so whenever you see the possibility to ionize things off of cyclobutyl, they're actually a little bit slower but they end up giving you this very similar kind of carbocation. They give you the same type of carbocation that looks like a cyclopropyl carbynol. Okay, so cyclopropane bonds are magnificently strained. They're super nucleophilic. Yes? Yeah. No, that was supposed to be, yeah, so when you have this cyclopropane here, it's now a thousand times slower. And if you make it without the cyclopropane, that's relative to the one that has no cyclopropane here. Because this bond has less P character. Note that this bond is outside the cyclopropane ring. Those bonds that are out sticking off the edges of the cyclopropane, those bonds have less P character and are less nucleophilic. It's the bonds within the ring that have more P character. And these aren't overlapping in space with that empty orbital. Is that? Yeah, in this case, this is within the ring. This CC bond is within the ring. So when you synthesize this derivative that has a CC bond here, this CC bond is within the ring and so super nucleophilic, screaming hot nucleophilic bond there. By having this carbon-carbon bond be part of a three-membered ring. Okay, so let's talk about a different type of nucleophilic bond. So everywhere, look for cyclopropanes and leaving groups next to them. Better than a t-butyl, better than a tritle cation, just to have one cyclopropane bond nearby. I want to draw, I want to remind you of the effects of making bonds longer. What happens when I take a bond and I make it longer? And I just want to compare the canonical molecular orbitals for bonds where, for example, I simply make things longer. So let's go ahead and start off by thinking about a carbon-carbon bond. And this will be a t-butyl group here. I want to do that so I can keep things similar. So I want to think about the orbital for that bond. There's a sigma CC orbital for this that's filled. And there's a sigma star orbital that's equally higher in energy for that CC bond. And so what happens if I drop from carbon down to the next row of the periodic table from carbon to silicon? What happens is the bond gets longer. So let me try to emphasize that in some ridiculous way like this, just so you can see. So you can't have SIH3 easily. So the values are reported for trimethyl. But the prediction is that this bond is longer. It's less stable. There's less orbital overlap, less effective orbital overlap. The bond is less stable. That means it's higher in energy. And that means the sigma star orbital is lower in energy. That's not so important. What's important is that this is now higher in energy. And if I drop yet one more, if I drop further below the periodic table to tin, let me make this even better. Even, I don't know if that looks longer. Then your expectation is whatever silicon does, tin can do better. Anything silicon is known to do, a carbon-tin bond is better at it. They're more nucleophilic. They stabilize carbocations more. They're more toxic, I guess. They stink more. They always do things sort of one-upping carbon-silicon bond. Your prediction is that carbon-silicon bonds should be super nucleophilic. Longer bonds are more nucleophilic. So let's see the implications of that for stabilizing adjacent carbocations.  So we've talked about before the effect of these CH bonds on a T-butyl carbocation. It's these CH bonds that are stabilizing a T-butyl carbocation. If you compare that to a T-butyl carbocation that has just one single carbon-silicon bond next door, so trimethyl silo, everything else the same. With that single carbon-silicon bond there, with that trimethyl silo group, this becomes more stable by 38 k-cals per mole. So how many times more stable is this when it has this carbon-silicon bond at the beta position? We call this a beta silo cation. Two words, beta silo cation. How many times more stable is that? I mean, whatever that is, divide by 1.4, it's 10 to that power. So that's something like 20, some 10 to the 20, something or something like that. It's a huge amount more stable, 10 to the 20s, something more stable. If you convert this into factors of 10, it's a massive increase in stability. So look for reactions that can generate beta-silocarbon cations. Now what I'll tell you is it is actually not very common to generate beta-silocarbon cations through SN1-type ionization reactions. But as we go through this course, what you're going to find is later on, you're going to see 100 million reactions that generate beta-silocarbon cations like this. And we'll get to this. This is the way you most commonly see beta-silocarbon cations formed in organic synthesis. Every time you see an allylsilane or a vinyl silane, you need to be thinking about how smoking hot, maybe I shouldn't say hot, it's how incredibly stabilized this carbocation will be. That's not just a regular double bond. That double bond can make a beta-silocarbon cation. So look for a little exilanes. Look for a little exnanines. Look for any chance you have to put this long carbon-silicon bond next to a carbocation. Okay, so this is not just the carbon group. It's not just carbon-silicon tin. Any longer bond is more nucleophilic. And so that means every single time you've seen a metal and it doesn't matter whether it's palladium or cobalt or rhodium, every single time you've seen a metal that has a chance to have a beta-carbocation, that's going to be a super stabilized carbocation. Let's all draw this there. So all beta-metal carbocations are stabilized. So carbon metal bonds are longer and they're very nucleophilic. Yeah, the bond is longer. So if I have a longer bond, it's higher and it's less stable, it's higher in energy and if it's higher in energy, it's more nucleophilic. Hyperconjugation means that this bond is donating into the empty orbital. That's just a different word for what we're talking about. I have to go look at that. Here's why it's complex. So if I put silicon here and carbon here, I still have longer bonds. The problem is that this is now farther away from the carbocation and I can't remember. I've looked that up before and now I can't remember. It's nothing special. I can't think of anybody who ever puts leaving groups alpha to silicon and gets a beneficial effect at it out of that. So my intuition is that no, it's not. The fact that this bond is longer doesn't make up for the fact that this bond is longer and it's farther. You have to donate way a longer distance over to the empty P orbital. Okay, so some bonds can be very nucleophilic and can very much stabilize carbocations. That's the whole point of that lecture. So now let's go on to a new topic. Or maybe it's the same topic. It's just a thousand different ways you can donate into an empty orbital.  My hope is that you'll be able to take these ideas of long bonds, strained bonds, those kinds of ideas and apply them to other kinds of empty orbitals like pi star and sigma star. When we get there. So I want to talk about some other types of groups that you can have next door to leaving groups. And that's the main idea here. And I want to start off by talking about a topic that we've already talked about. And that is what about heteroatoms?  And so, yeah, there's an oxygen lone pair up on top. That's okay. Don't worry about that. The main point I want to make is what's the effect of having another heteroatom right here? And let's put this into the context of DNA and RNA. Or this could be NAD plus. It's an enzyme cofactor. So what would you predict about the ability to this, for this base in DNA or RNA, purine or pyrimidine, to act as a leaving group? How easy? This is a source of mutations in DNA. What's the effect of having a hydroxyl group here? Does that make it faster? Does that make it slower? What we said is that these lone pairs are never nucleophilic enough to bend over and push out the leaving group. The only effect of having an alkoxy or hydroxy group next door here is that this slows down. This is an electronegative atom. It makes it harder for you to form an oxocarbenium ion, a carbocation at this center. So this ends up being slower. And it's about 150 times slower. I mean, it's not a factor of 10 to the 9 or 10 to the 20, but that's still significant. It's slower to depurinate or lose the pyrimidine or the purine base from RNA than it is from DNA. When nature made nicotinamide, adenindynucleotide cofactors where there's this leaving group built in, this is the base that's attached to NAD plus. Nature made it with this extra hydroxyl group here. It didn't use a DNA fragment to make that. That slows down the loss of that group. Not ever do you want that group to act as a leaving group for cofactor type reactions. So that's the effect of having this hydroxyl group as it slows down the loss of this leaving group here. So oxygen is not what you want to have at this visceral position, visceral to your leaving group if you want to have a fast ionization reaction. But that's only for oxygen. Let's see what happens when we switch to nitrogen. It kills me. This is a clinically used anti-cancer drug sold as mustergen.  It's very toxic. You can design something better than this. I'm positive of that. The whole idea behind this anti-cancer drug is this. This nitrogen is not oxygen. Nitrogen lone pairs are dramatically more nucleophilic than oxygen lone pairs. And if you have a nitrogen and a mean that's visceral to your leaving group, that can help push out. And it's not the nitrogen carbon bond. It's the lone pairs that help to push out that leaving group. And so what this does is it makes a strained aziridinium. So it's not an aziridine. It's got too many bonds. So you call it an aziridinium, kind of like ammonium. That's an aziridinium ion. And this now has strain. And that strain allows it to be opened up relatively quickly by nucleophiles like DNA. And so this leads to not just a single alkylation event. Those are very easily repaired by cells. But what it does is it cross-links because now after this opens up, you can imagine the same thing happening on the other side. And those types of cross-links are virtually, let me draw the DNA up here because I've run out of room. So now the same thing can happen on the other side and you can cross-link another strand. And those types of problems with DNA are virtually unreparable. Cells kill themselves. They undergo apoptosis if that's a problem. So nitrogen lone pairs, yes, they can participate in what we call neighboring group participation. Whereas oxygen isn't helping. The oxygen lone pairs are less nucleophilic. You couldn't have known there'd be that distinction. You couldn't have known that the difference in nucleophilicity for a nitrogen lone pair is enough to allow it to make those strained rings. So if you're looking for evidence that these things, more evidence that these kinds of aziridinium ions are important intermediates, if you synthesize this kind of chloroamine and there's nothing special about the chloride, it would be the same if you made the toslate. And you do substitution reactions with this where you have some sort of a nucleophile. This is one of the products that you get. Let me draw some stereochemistry here so you can see what's happening. It'll be completely inexplicable to you why you would get a six-membered ring product unless you know about this aziridinium ion formation. So you can tell what's happening here. What's happening is that this lone pair is helping push that out to make a three-membered ring and then the nucleophile opens up on the other side. So in fact, you get a mixture of both substitution products from this. And I'm not going to draw the intermediate. I'll leave that to you to draw the three-membered ring aziridinium ion in that case.  So just to put some, I'll bring this back to acidity and basicity. Let me take this off. I'll just, so if you look at the relative basicities of these lone pairs, you can go to a pKa table and look up a protonated oxygen versus a protonated amine. And the pKa's will tell you the relative basicity of those lone pairs. And so in terms of relative basicity, the pKa prime, pKa prime means if I put a proton on there, for this is on the order about minus 2 to minus 4, depending on whether this is R or H. For an ammonium ion, it's 10. That's the pKa for a lysine side chain or triethylammonium, those sorts of things. 12 orders of magnitude difference in basicity. This is 12 orders of magnitude more basic and approximately that much more nucleophilic. Yeah. Oh, because oxygen's more electronegative than nitrogen. So oxygen's electronegative. There's more protons in the nucleus. And because this is more electronegative, if you try to make a carbocation, when there's an electronegative atom here, it kills you. It's really bad if this is fluorine. It really destabilizes that carbocation to have an electronegative atom here. Yeah, like without it, it's faster with the hydrochloride. Yeah, it's electronegative. So if you have an electronegative atom here, the lone pairs aren't helping you. All you get is the bad electronegativity of oxygen that's destabilizing the carbocation. So, yes. So put it in the mean right there on that position. Yeah. If it's anti to the leaving group, it'll help push it out. Okay, so let me, where did this mustardion thing came from? It came from people trying to kill each other. So these are casualties due to chemical warfare agents in World War II. I mean, and here's one of the principal chemical agents that they were lobbing back and forth at each other during, sorry, World War I, during World War I. And this is not a nitrogen mustard. It was a sulfur mustard. So when you hear people talk about chemical warfare and mustards, they're referring to the sulfur compound. And it turns out that it's like, where does sulfur fit in? Is that like oxygen? And the lone pairs don't push out leaving groups? Or is it more like nitrogen? Well, sulfur's in the same row as oxygen. It's called a chalcogen. But because these lone pairs, because the sulfur is, the bond is long, the lone pairs are bigger. Everything is bigger. Bonds are longer. The lone pairs are bigger. These lone pairs are more nucleophilic on sulfur. And so it turns out in this case, you do get neighboring group participation for sulfur, for selenium. Once you drop below that second row, also, sulfur is not as electronegative as oxygen. So you suffer less of a penalty in ionization reactions. But when you pop this thing off, you end up generating this, what looks like a weird species here. This is not, it looks kind of like an epoxide, but it's not an epoxide. If this were neutral, we'd call this an episulfide. But it's not even an episulfide. There's a positive charge there. We call this an episulfonium ion. You don't call a protonated epoxide an episuponium, I don't know what you'd call it. But it's like an epi, it's the name comes from something like epoxide, but it's a sulfonium ion. Okay, and then in the presence of water in your lungs, unfortunately, this opens this up. And I won't show all the steps. But the important point is you start cross-linking proteins, mainly, it's too fast. This is too fast to happen and wait around for DNA. This starts to generate two moles of HCl gas for every one of these, for every one of these molecules that gets in your body, and the HCl causes edema and starts blistering your skin, very bad stuff. Okay, so sulfur is more like nitrogen. For a different reason, the sulfur lone pairs are more nucleophilic than oxygen lone pairs. Why is that slow? Yeah, sterics, which is very hard for nucleophiles to attack at tertiary centers. So keep that in mind. So let's put a thioether right next door to that o-tosylate. We can see those lone pairs are ready to help push out. Just like I told you, those lone pairs are ready to help push out this tosylate. If you look at the products you get out of this reaction, you get two different products. If you use ammonia as your nucleophile and you get those products in a 4 to 1 ratio. So let me go ahead and draw out that episulfonium ion intermediate that you generate. So the reaction starts off with this ionization reaction where the sulfur lone pairs are pushing out the leaving group. And so you get this episulfonium ion. And now, if you're using an amine as the nucleophile, in this case ammonia, that ammonia has two choices. The ammonia can attack over here at the primary position or it can attack at the more substituted position. And you can tell from the products that the dominant mode of attack is for the amine to attack at the more substituted position. That's the general rule. Nucleophiles attack at the more substituted position. When you have positively charged three-membered ring-onium ions. So if you learn some sort of a rule in sophomore organic chemistry that, oh, you always attack more quickly in SN2 reactions at primary or at less substituted positions, that's wrong. And it's wrong in this case of three-membered rings. So let's be clear about where this is true. So if you have an epoxide like this, it's faster to attack at the primary position. If you protonate it, it prefers to attack at the tertiary position. Yes, it would still attack at the, it doesn't go through a carbocation. So if you make an, a quaternary ammonium, notice that there's a positive charge here. Nucleophiles prefer to attack at the tertiary position. If you have the episulophonium ion, and again, it doesn't matter whether it's quaternary or, you know, whether it's secondary or tertiary, nucleophiles attack at the more substituted position. If you have a mercurinium ion, we don't cover oxymercuration reactions anymore. We used to cover those in, in sophomore organic chemistry, but mercury is toxic. These will prefer to attack. You always get attack, what we refer to as Markonikoff addition of the nucleophile to the tertiary position. It's opposite if you don't have the positive charge. The effect of this is that you're really, the, I'm, maybe I ought to be exaggerating these structures in a way that helps you to remember this, but this bond is just a lot longer when you have these onium ions. It's already prebroken before the nucleophile comes in. So, yes, it is sterically encumbered to attack at that tertiary position, but the bond is already partially broken in all of these three types of structures. So, this is the general rule. So, it's only when it's a neutral three-membered ring that you attack at the less substituted position. What if the more, meaning that what if you had something like this, and it was maybe over here, but very bulky? And then, let me try to make it equal. Let me try to put another group on this side. So, now they're both secondary. I'd predict you'd attack here faster. Maybe you can ask me afterwards, and then I'll try to answer that. So, I'm not getting it, but you can ask me afterwards. Okay, let's look at some other, and I've just finished covering a bunch of examples where you make strained three-membered rings. And let me step away from that, because it's not like every neighboring group has to make a strained three-membered ring. It is kind of surprising, isn't it, that you can have neighboring groups that will readily form three-membered ring intermediates. One thing I want to urge you not to do, and I'm going to do this, and you just have to remind me to, hey, stop doing that, is I want you to stop calling these, or if you're about to, to not call this an SN2 reaction. So, if you do some substitution of this by some nucleophile, that's not SN2. By definition, SN2 means that the transition state involves both nucleophile and the electrophile. They have to collide 10 times higher concentration of nucleophile means 10 times higher reaction. That's the definition of SN2. Rate equals rate constant times concentration of Rx times concentration of nucleophile. By definition, this is an SN1 reaction. So, I don't have an alternative to this SN1, SN2 language and nomenclature that we use, but the whole SN1, SN2 system breaks down when you want to describe this. That's not SN2. That's actually an SN1 reaction, even though it involves a concerted displacement. Okay, let's take one more, one more example of neighboring group participation that involves lone pairs. You draw two different substrates that have toslates here, and in each case, I'll draw it. There's an acetate group that's nearby. And, of course, oxygen is electronegative, so maybe that's not so good, but you can get a beneficial effect out of this. And it matters stereochemically the way that neighboring group is disposed. So, if I look at the relative rates for ionization, for popping out of this toslate group, what you'd find if you measured the rates at which toslate leaves from these, you'd find that this other isomer over here, the anti-isomer, is 600 times faster. It's 600 times faster to have the anti-isomer. And you can kind of guess the reasons why. I'm going to start off by drawing this in a confirmation that can help you see what's going on. This chair can flip back and forth between different chair type confirmations, and it will eventually reach a confirmation in which this toslate is oriented where this carbonyl lone pair can help push that out. And unlike all those other examples that I showed you, if you think, oh, but this doesn't look so good, there's those axial bonds, but this ring has none of that strain of the three-membered rings. So maybe it has to generate a small amount of this diaxial conformation, but now there's nothing stopping this. There's no ring strain stopping this from cyclizing around to give, and now I'm going to draw this with a flat structure, to give an oxonium ion intermediate. So here's the intermediate that you would get in this reaction. You would now have the, I'm just now realizing that I'm, I think I'm drawing the enantiomer of this. So don't, if you want, you can make this dashed and dashed and bold and dashed. Sorry about that, I didn't mean to do that. So you get this intermediate. Now where essentially you can draw an equivalent of the resonance structure with the double bond here. So that's an oxonium ion with three bonds to oxygen, this particular resonance structure. And so now the nucleophile, in fact, can attack either side of this. You'll see 50% of the attack occurring here, and if you draw the other resonance structure, you can see why the other 50% of the attack occurs down here at the bottom. So you get both enantiomers out of this. So ultimately you'll end up getting, if you're doing the reaction in acetic acid, so let me write this down with the, I'll write acetalysis to indicate that my nucleophile here is acetate. So in the end, you'd end up with half of your acetate anion attacking here, half of your acetate anion attacking there. So you get a racemic mixture, even if you started with one in, with a single enantiomer of your substrate. Okay, so that's neighboring group participation by lone pairs. We're going to have to stop there. And when we come back, we're going to consider a little bit more what it's like to have double bonds near leaving groups, not directly adjacent where you can form a carbocation, but somewhere just a little bit farther away. Can you have double bonds poised somewhere else to help push out leaving groups? And of course the answer is yes. And we'll see how much that can be worth in terms of rate accelerations.


I have my own personal step, which is great. I'm going to just shove it over a bit. Brilliant.  I'd like to start by asking how many of you have experienced a mental health issue in your life?  Lots of hands. Keep your hand up if you found it difficult to talk about it. Again, lots of people. Thank you. Over the last year, around one in four people in our country struggle with a mental health problem. That's almost a quarter of the people in the room, which is roughly the number of people that put their hands up. In any given week, one in six of us reports experiencing a common mental health problem, like anxiety or depression. If you're a man aged between 20 and 49, the most common cause of death for your age group is suicide, which is deeply shocking.  That's one person every 40 seconds. Globally, suicide is the leading cause of death amongst 15 to 29-year-olds. Mental ill health costs the UK economy 99 billion a year, and it's responsible for 91 million working days lost a year. That's more than for any other illness. All these worrying statistics are framed by the fact that only 40% of people with diagnosed mental illness received any treatment or access, any help at all. This is the context within which mental health first aid, the organisation I led for 10 years, was framed. We wanted to change attitudes to mental health, to remove the negative association surrounding it, to lose the stigma. We wanted to make it easier for people to talk about their difficult feelings and thoughts without fear of the consequences. We're used to having physical first aiders in the workplace, colleagues trained to help us with the physical injury. Our aim was to have mental health first aiders working alongside them. People trained to recognise signs of mental distress in others. People who know how to confidently approach someone and start a conversation. People who know how to listen non-judgmentally and who can help those in turmoil find the support they need. If we could get this right, we believed that the world would be a better place. In my 10 years of being a mental health first aider, I've used my skills to support hundreds of people, including myself and my family. I don't know how many of those conversations were life-saving, but I'm sure that every conversation moved that person one step closer to recovery from a place of shame to a place of hope. And I'd like to share with you what hope means to me. I'm second generation British Bangladeshi. My grandad came to Portsmouth in 1959, having served in the merchant navy for 20 years. At the tender age of 12, my dad joined him. They worked hard to provide food, shelter and education for the family back home. As a result, my dad lost his childhood, and a few years ago he passed away at the age of 64, robbed of his old age too. He was part of a generation of lonely young men who sacrificed everything to create a better future for their families. I was born in Bangladesh in a house made of mud and straw. It was small and crowded. We had no electricity, no sanitation or running water. My grandad migran myriad chickens to buy her first bit of and sold eggs to buy her first bit of Paddyfield to grow rice in. My mum was just 14 when she married my dad on one of his rare visits to Bangladesh. She was 15 when I was born and my dad was back in England. We joined him in Portsmouth two years later. So here you have a young couple without role models or the support of an extended family doing their best to beat poverty, raise children and have a sense of identity in an environment where nothing feels familiar, especially the language. You can understand why preserving their values, culture through food, religion, language, marriage customs and gender roles was so important to them. They struggle, they adapt and they find a place in their migrated life that sort of works for them. And then I, the eldest of three, hit my dreaded teens. I was an intelligent, ambitious, bollywood loving, dance loving, religion hopping, contradiction filled, no at all teenager, trouble and extremely troubled. The constants in my life were some my school routine and some unforgettable teachers who made a lasting impression on me. Some were racist, motivating the activist in me, but others opened up my world, inspired me, helped me dream and led me to believe that anything was possible. I became skilled at managing multiple parallel lives. I was head girl and I bunked school. I was a grey day maths and science student with ambitions of becoming an electronics engineer, yet I knew I'd be lucky if I was allowed to go to college at all. I was my mother's main support yet I was self harming. As a parent now I know I was every parent's nightmare. So eventually my risk taken behaviour got so bad that my parents decided it was time I was married. So at 17 I was made to marry someone six years older than me, who I met for the second time on the day of our wedding in a country I didn't recognise as home. A couple of years later I became a mum and also got my first diagnosis of depression. I wanted to be a good parent and I wanted to die. Life was very dark for a while. I got really ill and scared that I might lose my child to poor parenting so I left my marriage I couldn't afford to be ill. I was a single parent and I was driven by my need to be a good mother. I knew I had to achieve financial freedom. Poverty as a single parent was not an option either. Like my dad I too lost my childhood to work, parenting and mental illness. I often wonder what difference a few good quality conversations would have made in my childhood. Conversations like the ones mental health first aiders are skilled at and my parents could have been helped by them too. I believe mental health first aid is a success because it's built on thousands of stories like mine. And it's really important that our stories are heard. It's not about the particular things that happen to me. It's about the fact that I experience depression, anxiety in response to them, which is a common part of human experience. I also wonder where I'd be now without the support I'd got when I needed it most. Those small acts of kindness that made all the difference to me. The health visitor who noticed that behind my mask of coping with young motherhood I was falling apart. She took me away from the bustle of the busy health centre waiting room. She encouraged me to look closely at the healthy happy baby I'd bought into the world. She assured me my daughter was fine and then gently asked me how I was. I broke down in tears and she cared enough to take action. She went against the grain of normal practice and found a doctor to come and see me straight away. An act of professional kindness that set me on my road to recovery. On another occasion I found myself wandering along a deserted windswept beach thinking of ways to put an end to my emotional pain. Lost in thought I tripped and fell. I wasn't particularly hurt but I was upset. I thought I was alone but out of nowhere a stranger appeared. He approached me carefully, respectfully with open hands. As if to make it plain I had nothing to fear. I wasn't afraid. He asked me a simple question. Are you okay? I noticed you fell over and you're crying. I told him I think my life is over. What I said startled me. I sat down on the stony beach and he sat down beside me. Neither of us said a word. We didn't even look at each other. We just sat there watching the waves. I felt supported held by his compassion. After a while I got to my feet, thanked him and went home. I never found out who he was or saw him again. But I'll never forget how his simple act of kindness made me feel. The most important part of my work is encouraging people to look carefully, to notice. Without the simple act of noticing we can't begin to reach out or give support. The people who helped me may have been doing their job well. Or being their authentic compassionate selves. But the impact their simple acts of kindness had on me was life changing and life saving. Thanks to them I stand before you today as a leader in the mental health sector. It's a reminder that who we are and what we go on to achieve is built on a bedrock of support from those who we come across in life. Family, friends, teachers, colleagues, coaches, mentors, health workers, kind strangers, simply too many people to mention. In the words of the old saying it takes a village to raise a child. And I'm proud to say that mental health first aiders make a vital and positive contribution to the many villages that make up our world. We teach others to notice when someone is in distress and encourage them to reach out, listen and offer support. We should never underestimate the life changing potential of such simple acts of kindness. Sometimes I wish I could go back and thank all those people who changed my life for the better. But then I remind myself that the work I do now is paying it forward which is the best possible way of honouring them. Work played a vital part in my recovery from poor mental health. Even though I was ill my intuition told me I needed routine and purpose. So when my daughter was just three weeks old I went for an interview and got the job. It was a part time role at the Citizens Advice Bureau which paid less than being on benefits at the time. But it gave me what I needed to kickstart my life. Soon I was working for adult mental health services in a community team. We set up and run services for people coming out of hospital care. My team helped them gain confidence with everyday things like shopping, cooking and paying bills. Around this time my manager Fiona suggested I joined a leadership and career development program. I didn't think I was up to it. After all I was just a school leaver with mental illness. I was doing well managing a small team in the community on a basic salary. Who was I to think I could be anything more. I was paralysed by the imposter syndrome. A persistent voice inside my head telling me it was only a matter of time before I got found out. But Fiona knew what I needed. Looking back I realised Fiona saw something in me that I was unaware of. I could hardly believe it when I got a place on that program. A program that was to profoundly change the direction of my career and my life. I found myself in a room full of people that looked like me. We talked about the way race and gender discrimination had affected us. We shared how we saw the world and our place in it. For the first time ever I understood how being an Asian woman in the UK had affected my mental health. The journey of self-discovery was both disturbing and strengthening. I felt like my new roots had been nourished and nurtured. I stepped into my identity as a British Bangladeshi woman. Until then I'd always felt like a visitor because my parents had raised me as one. A common narrative in migrant communities. The leadership program also gave me the chance to develop a personal vision. A vision of a world where mental health is no longer seen as the poor relative to physical health. I wanted to raise my mental health awareness through education on a global scale. Seven years later that vision started to take shape when mental health first aid England was born. Just as my recovery from mental ill health wouldn't have been possible without those simple acts of kindness from others. My vision would never have seen the light of day without mentors to guide me. Fiona was one but I'd like to tell you about two more. First, Sheila. She was the chief executive of Portsmouth Mental Health Trust where I worked. She was a role model for me. Somehow she managed to combine being a successful chief executive alongside a nurturing of family. She was a busy woman but despite the demands of her job she made time for me and encouraged me to apply for a job I thought was beyond me. I was fuelled by her belief in my ability and skills. She talked to me to take risks and worry less about failure. To my amazement I got the job. At the Department of Health surrounded by exceptional people I started to find my professional voice. I was the lead on three national mental health programs. Then there was Richard, my new boss, another person who took the time to mentor me. One day Richard asked me about my career plans. I told him I felt like an imposter surrounded by academics and doctors. He agreed my CV needed work as it didn't reflect my skills and experiences. He said fine, if you feel like an imposter let's get you a qualification. So I enrolled on an MBA which thanks to Richard the department paid for. Richard has had a profound influence on the way I manage others. He taught me that leadership is about developing people for life. Not just the role jobs they're in now. It's about helping people realise their potential. Helping them be the best that they can be. It's about taking a chance. I learnt a lot on that MBA course but was puzzled by something. Why was business success only measured in terms of money? I couldn't understand why we were not being taught social value. Why the bottom line only spoke about profit. Why leadership barely touched on purpose. In 2009 I got my chance to create an organisation that challenged that and received wisdom. Mental health first aid England a community interest company was born. A community interest company operates like any other business. It generates profit or surplus as we like to call it. That surplus is reinvested back into the community interest. Which in our case is to increase mental health literacy. Back in 2009 we were optimistic and idealistic. Little did we realise what we'd let ourselves in for. In year one we made a loss which was not surprising. However in year two we made an even bigger loss. I lost sleep and weight worrying about it. But since those early days our business has gone from strength to strength. Today the London office is home to a team of around 65 full time professionals, 45 national trainers, 120 associates, 2,000 instructors and a community of 350,000 mental health first aiders in England. There are almost 3 million mental health first aiders globally. We've trained people from all walks of life. Some of whom are quite well known. Government ministers like Norman Lam, Jeremy Hunt, Sadiq Khan and the Mayor of London, Prince Harry while he was serving in the armed forces and last year I was invited to Downing Street to brief the Prime Minister and her cabinet on World Mental Health Day.  They recognise that if they want to attract, retain and grow talent they need to create healthier workplaces. And we've taken an active role in the wider world too. We've helped develop mental health programmes in Bangladesh, Tanzania and Uganda. My own struggles with mental ill health gifted me insight. My community development routes gave me my moral compass. The leadership programme gave me the opportunity to think about my vision for the first time in my life. The MBA taught me business acumen. They all came together to give me the knowledge, confidence and energy to lead mental health first aid England. For us making a profit always came second. We regarded it as necessary but not sufficient measure of business success. In 2016 we were recognised as the ninth fastest growing women led small business in the UK. In 2017 according to the FT we were one of Europe's fastest growing companies. This year as I left my role as the CEO of mental health first aid England we closed our accounts at £5.7 million revenue and £800,000 profit. But as I reflect on the journey so far, the thing I keep coming back to is the kindness of others who helped me along the way. Without the people who encouraged me, believed in me, took a chance in me and backed me, I'm convinced I wouldn't be standing here before you today sharing my story. So take a moment to think about the people in your world. Who could benefit from your support and encouragement? Sometimes it's just a kind word. Sometimes it's about giving your attention and time. Running an ethical business is about looking out for each other. It's about making sure we put more into society than we take out. It's about creating a business with heart, which is also a great place to work. Work doesn't just provide us with money. It gives us our life meaning and purpose. It can make us and those around us happy. It can be good for our mental health. The ancient Greeks had a word for it, eudaimonia, which means both human flourishing and prosperity. My experience, human flourishing, is not only compatible with business prosperity. It's essential to it. Thank you.


headline news update. Welcome folks we have the Dow industrials finished down three twenty two Nasdaq off three eleven S&P's down fifty one we take a look at this percentage wise what you have out here folks is that you're the Dow industrials trading down one point no actually nine tenths of one percent Nasdaq down two point one four S&P's up one point two three gold gold contract up ten dollars seventy cents trading out at seventeen eighty seventeen sixty nine gold broke its downtrend last week wants higher price silver up fourteen cents twenty two dollars sixty eight cents light sweet crew whether whether the light sweet crew is amazing folks up about sixty eight trading seventy seven fifty six we're an inflation man and these numbers are inflated and what does it mean it means we're going to be paying higher price and I don't go for this deal that you know the bottom line is going to back down it's transitory yeah where we're at higher price notes and bonds that ten year note down five ticks trading one thirty two flat the thirty year off eleven at one sixty flat and king dollar king dollar down two hundred forty six ticks trade ninety three seven eighty nine king dollar does look like it's going to get back inside this lower range if that's what you get hold on for the ride inside the commodity markets folks because if this fails you're going to see the dollar make its way to lower end of the consolidation which is the eighty nine five hundred mark and that'd be a monster move easy to make sense though because the bottom line the euro it got killed the yen had got well the euro got weaker against us dollar the pound got weaker against us all the yen got weaker against the u.s. dollar and the bottom line those have all reversed also so now they're looking to all get stronger against the u.s. dollar and if that's what we get that u.s. dollar will get under this breakout area which is the ninety three four fifty area that's only three hundred ticks down and we're down to forty eight today we didn't let's go look at the end the X one hundred first my take is that we're going to bounce out of here if you've been listening to the show we'll see how this shakes out we made that your price projection of three fifty two the abc down your benchmark was three fifty two oh four we close that three fifty two sixty nine after trading to three fifty thirty two so I suspect we're going to bounce out of here that being said you can see that we have seventy three million shares today versus the high volume low sixty four so now you have another high volume low more than like you're going to do a B to a C of another ABC structure on the way down have a great night folks have a safe night come back and visit Tommy tomorrow morning kicks us off nine o'clock in the morning great show have a great one folks have a safe one


Hey, this is Brett and this 2013 Chevy Equinox LTZ all-wheel drive is stock number 24T45C. I am here at Summit Automotive in Fond du Lac, Wisconsin, you're new and used SUV headquarters. This 2013 Chevrolet Equinox LTZ has the 2.4-liter four-cylinder engine. It's paired up with these six-speed automatic transmission, puts out 182 horsepower. This vehicle has been fully safety and inspected by our service shop, has a fresh oil and filter change. All the fluids have been checked and topped off. It has four brand new tires and this Equinox is 100% ready to go. I'm going to go all the way around in this video inside under the hood, start it up, show you all the options and just give you the most accurate representation that I can of the vehicle. This little red tint coat is a color. I shoot all my videos in 4K. If you like the video, subscribe to the YouTube channel, click the bell notifications, get updates on the videos I do each and every day as well as having access to one of the largest catalogs of vehicle walk-arounds on YouTube. This one comes with the alloy wheels with the chrome covers. These are 18-inch wheels and it has brand new CUMHO EXTA 235 55ZR 18 tires. They still have the knobs on them from being brand new. This is a clean title history, clean car facts from Wisconsin. We put the tires on in our safety inspection. Front fenders in excellent shape. Headlight lenses are nice and clear. You get the projector style headlamps, projector style fog lamps. I'm going to turn all those on at the end of the video so you can see just how bright they are. You get the chrome trimmed grille and the hood is in fantastic shape. I didn't see any major dents or dings on there. Passenger side front fender is in excellent condition. And the passenger side front wheel does have one little scuff on it, but for a used vehicle with this many miles, pretty nice shape. That tire is brand new as well. Crystal red tint coat. It's got just a little bit of metal flake to it. Light up on it, paints in really nice condition. As you go down this side of this 2013 Chevrolet Equinox, take a note of how clean the body is, how reflective and mirror-like that paint is. Take these HD videos so if you're far away or even if you're close by and you just cannot make the trip down, but you're still interested in purchasing the vehicle, you can see the vehicle, hear the vehicle, and have confidence in what you're looking at before you even get here. So when you do get here, there's absolutely no surprises and you can make a smart and informed buying decision from wherever you're at. If this video helps you make that buying decision, let your salesman know. Just saw the video. It was helpful and that Brett sent you. The back wheel cover is in pretty nice shape, a couple little scuffs on there. Nice thing about these wheel covers, they're easy to replace and not that expensive. Back tire is brand new as well, and four wheel disc brakes on this vehicle looks like the back brakes are brand new, which we would have done in our inspection. Coming around to the back of the vehicle, the rear bumper is in pretty nice shape. It does have the backup parking sensors, no major dents, dings, or cracks back here. A little receiver hitch with four pin wiring, probably for a bicycle rack or something like that. The rear gate is in pretty nice condition, I didn't see any major dents or dings on there. It is a power lift gate. You can see that works nicely. Back storage area is in very nice clean condition, I do believe that is a subwoofer.  Those seats do fold down for extra storage, I'll show you how that works as well. To get this gate down you press that button and it will come on down like that. Only thing really to note, there's a couple little chips in the paint, a little bit of corrosion, nothing too bad though. Coming around the driver's side, just as clean as that passenger's side, no major dents or dings on the door rear quarter, and for full disclosure, this back wheel of the same condition as the rest, a couple little scuffs there, nothing too bad. Down the rest of the side, other vehicle doors look really good. It does have the heated power mirrors with the blind spot mirrors, chrome trim on the back of those mirrors. Take a quick look at the back seats. Second row seats are in excellent condition, no rips or tears back here. It does have the latch, child safety system for any child car seats you may have. Factory floor mats, carpeting is nice and clean back there as well. And you can see just how nice and flat those seats fold down. There's actually a plastic thing here, so if you need to slide stuff up, nothing's going to get trapped behind there. And you get, I believe the child safety locks are on the front door. Bottoms of the doors look pretty good. Pretty typical things going on with the Upanox, they're a little bit on the bottom of the doors, but four to miles on this thing, very nice and clean. Front seats, you get the black leather buckets, both these front seats are heated. No rips, no tears on these seats, they're in pretty nice shape. Power driver seat with memory driver seat, factory floor mat. Power windows locks and mirrors, you get the Pioneer premium sound system, will hop inside. Check out the miles, radio and everything that this one has to offer on the interior. You can see this one has 75,715 miles on it, you do get the digital speedometer, compass display, instrument cluster is very nice and clean. This one comes with the leather wrap steering wheel, Bluetooth and audio controls on the right, cruise controls and forward collisional warning and lane departure warning controls on the left. You get the Chevy MyLink radio, it does have AM, FM and Sirius XM radio capabilities, you get all these different apps on here. This one I believe has the factory navigation system and you can see that is working nicely, there's highway 41 and this is also where your backup camera shows up and I believe the vehicle has to be on for that to work. But also you get all these different apps on here and there you go.  Passengers side format and seat are in excellent condition, no rips or tears on there, smells very clean inside this vehicle. The headliner is in gray shape and it does come with a power sunroof. You get homelink buttons up here, map lights and on-star and SOS buttons in the mirror. Let's start it up and take a look under the hood. Starts right up, no check engine lights or anything like that. I would personally like to thank you for checking out the video today and hopefully from this HD video you've been able to verify the quality, condition, options and of course cleanliness of this vehicle all the way around inside. See all those lights are working nicely and under the hood we have the 2.4L 4-cylinder Eco-Tec engine, engine bay is very clean, runs very smooth. Once again this vehicle has been fully safety and inspected by our service shop, has a fresh oil and filter change, all the fluids have been checked and topped off, shocks doing a nice job holding that hood up. There is the emission sticker and this car is 100% ready to go. See more pictures of this vehicle in one of our 550 new and used cars, trucks, SUVs, minivans, Wranglers, you name it, we got to go to the website right there SummitAuto.com, full pictures and descriptions of every single vehicle all at SummitAuto.com. If you want to check out more HD videos you can go to YouTube.com slash SummitAuto. Click the bell notifications to get updates on the videos I do each and every day as well as having access to one of the largest catalogs of vehicle and SUV walkarounds on YouTube. Also stay current on our ever changing and vast inventory here at SummitAuto. In fact in a second you will see a link to subscribe to my YouTube channel on the upper left. A link to all the Equinox vehicles I've ever done in the upper right, a link to this vehicle on our website on the lower left and a link to one of our latest YouTube videos on the lower right. Check those, check us out, we're super excited to help you with this ultra clean 2013 Chevrolet Equinox LTZ and Crystal Red Tin Coat. Thank you so much for checking out the video. Remember to like, subscribe and share on the YouTube channel, I really appreciate it. Thanks again.


When I just moved to the United States from Morocco, I would talk to immigrants who have lived in this country for so many years just to help me understand the ins and outs, the dos and don'ts and things that I should avoid in order to have a decent living in this country. And everyone seemed to agree on the fact that I should not be spending money that I don't have, which I think is a great tip, but that made me stay away from using credit cards. I avoided them like I would avoid the plague. There are so many times where I only used a debit card. And then at some point of time, I started opening my mind to using credit cards. And I don't think I ever had more than two credit cards at a time, which kind of helped me become financially responsible and just be aware of where my money is going. But at the same time, I stayed away from using travel cards and leveraging points from travel cards to travel for free. And I can't believe that I was missing out on so much. I only started using travel cards about two years ago. So if you are like me, I'm going to explain to you how you can leverage points from travel cards and how the whole thing works. If it's something that you are already familiar with, you can skip to the next segment. So how does it work? How can you obtain or accumulate points to travel for free? There are some banks here in the United States that would offer you to open a credit line or a credit card with them. And they will ask you usually to spend a certain amount of money within a specific amount of time. And in exchange, they will give you a signup bonus. So for example, if you open this credit card with this bank, they're going to give you 60,000 points that you can redeem and use for air travel or hotels or cruises, so many options to choose from. And then in return, they expect from you to spend, let's say $3,000 in the first three months or something like that. And I know that it might sound like a lot of money, but if you look at your monthly expenses and then you use that card just to pay for whatever you usually pay money for on a monthly basis, like your groceries and some of your bills, you can easily get to that amount of money. And then as you continue using that card, you will accumulate points. So technically you are accumulating points on purchases that you would normally make regardless of whether you have a travel card or not. So why not take advantage of the points? And as you continue accumulating points month after month, year after year, you will have a considerable amount of money that you can use to redeem and buy your flights or at the very least can use them to reduce the cost on some of the flights or accommodation or cruises and things like that. There are two travel cards that I started experimenting with. The first one, and I highly recommend this one if you are just getting into using travel cards and that is the Chase Sapphire Preferred. They have an annual fee of $95 and I can put more details in the description box where you can read about how much money you have to spend on it. But I think it's a great card. I'm really happy with the perks like they have delivery in DoorDash for free. You get extra points if you are using Lyft and things like that. So a lot of good perks. And then the other one that I started also using is the American Express Gold Card. I'm really enjoying this card as well. So many important perks. I will have both of them in the description box if you are thinking about starting to experiment with travel cards. And if you use the link in the description box, I might end up getting some bonus points from their referral program. And if you do the same, if you open your own travel card and then you refer your friends or your family, you can also obtain some bonus points from this referral program, which is pretty nice. So as we speak right now, I think between these two cards, I already have just from this China bonus, I probably have $1,500 just sitting there that I can use to book a flight to Europe or just fly somewhere here in the US or go on a cruise, which is amazing. So I really can't believe that I've been missing out on using points and leveraging points from travel cards. And that is the first bad travel habit that I wish I changed early on in my travel career. Staying in hotels when I don't really need to early on in my travel career, I would go or travel to a new state, for example, and I'm going there to explore and do some hiking and backpacking a lot of times. The first night and the last night, I would stay in a hotel just to have a comfortable bed or have a nice shower, which there's nothing wrong with staying in a hotel if this is what you want and this is the type of experience that you are interested in. But I'm starting to learn right now that there are so many alternatives, especially if you don't want to spend that much money on travel. Definitely having your car, investing in some camping gear and relying on car camping can definitely reduce the cost of this travel. So it's something that I wish I had changed early on. And that is to not stay in hotels when I don't really have to because sometimes I felt like I was just spending so much money for one night. I'm not really enjoying being in the hotel. I'm just there to crash and sleep while I can be taking advantage of some free camping around the area in state parks or some Bureau of Land Management land or even pay for campgrounds because you can still pay for campgrounds as minimal as $15 a night or $20 a night. And that's a travel habit I wish I changed early on. Buying snacks on the road.  And then same thing, if we are going on a road trip stop at every gas station, get all of the snacks and all of the food that I need. It's that type of expenses that keep adding up slowly and slowly and slowly and slowly and then towards the end of your trip you just ask yourself, where did all of my money go? So instead right now, I try to plan everything in advance try to meal prep at home or at the very least buy my snacks from the grocery store from Costco and have everything ready so that I don't have to spend so much money on the road. It's something that I wish that I changed early on. Along the same line is buying water from airports and gas stations too. Oh my God, I've done it so much in the past and I'm the type of person who drinks a lot of water so I would go to the airport and if we are waiting I will end up buying two bottles of water three bottles of water and the same thing on the way back and if we are going on road trips I would buy so much water from gas stations and while right now I try to always carry my analogy water bottle and I try to carry my hydroflats can then just go to the refill stations at the airports and sometimes even when we are road tripping in national parks and states parks and more established campgrounds there are so many water refill stations where you can just fill as much water as you need so I am getting better at it right now but I wish I had stopped it earlier because not only it's a waste of money that keeps adding up quickly but also it's not friendly for the environment most of these water bottles are plastic and I'm just happier to have my reusable water bottle that I can use right now relying on air travel rather than road trips there are so many pros and cons of choosing air travel over road tripping obviously if you're gonna go on road trips you want to make sure that you have a reliable car that can take you from one place to the other without breaking it's definitely something that I didn't have early on but now that we have a car that's more reliable we're trying to explore more road tripping rather than catching an airplane to get to and from places and I'm really starting to find that road tripping or going on road trips is definitely making travel a lot cheaper and a lot more accessible not tracking flight prices I've always been good when it comes to taking my time to book a flight ahead of time and do my research and make sure that I'm finding that optimum sweet price but the one feature that I didn't take advantage of and by the way, I always use Google flight it's my go-to platform to find my flights I did a live stream in which I talk about the whole process and you can find that right here that's what I use to find cheap and reasonably priced flights but the one feature that I didn't take advantage of is tracking the changes in flight so this feature in Google flight allows you to go in you choose a specific flight, destination what dates are you interested in and then they start sending you notifications on a weekly basis to tell you this is how the price is changing so if you have like six months or seven months that you can play with to choose the right time to book your flight these notifications are going to show you how the prices are changing they can be very helpful to make a very well informed decision before you book your flight and finally buying souvenirs it's definitely a travel habit that I wished I stopped early on I used to buy so many souvenirs especially postcards not just postcards that I would send to family and friends because I still do that but buying postcards for myself or magnets for the fridge I used to do that a lot but now I feel like I'm more content to just take photos and save photos or maybe print them and put them on the fridge but I wish I stopped buying souvenirs in the past because A, it's more money that you are spending and then B, you just end up with a lot of clutter around your house and then it's not enough space on the fridge and it's a lot of things that you have to think about so these are some of the bed travel habits that I wish I had changed early on in my travel career I hope that you guys found some of them to be useful and I'm curious to hear from you what are some of the habits that you would like to change or some of the habits that you already left behind you let us know in a comment and if you found this video to be useful please give it a thumbs up consider subscribing to the channel my name is Habiba this is Trekking Pal and I will see you very soon on a new adventure


This is our LED tube and basically what differentiates us from the rest of the pack is that little sticker right there, the UL classification sticker, that means you can put it inside your UL listed fixture and still maintain your UL mark, so if you're looking to save energy first place to start is with your lighting. We've got actually four systems, we have a 65 and 80 and 120 gallon system. We have vacuum tubes which is very very efficient and high temperature. These vacuum tubes heat the water and then it's pumped through a pump and pumped into the tank. We have two coils in our tank, a lower coil and an upper coil and that coil is just think of a copper tube that's spun around in a circle and that's your heating element. It's very simple, very basic using pumps, low energy consumption, so therefore you're saving a tremendous amount of energy. These technologies have the potential for being some of the most environmentally benign in the world on our planet which has been misnamed to Earth, it should be called oceans because 70% of our planet is covered by oceans and using the power of tides and waves we can move forward towards a sustainable, reliable, affordable energy portfolio. Absolutely, Ice Energy is a Colorado based company doing manufacturing in New York and deploying in California and what we're dealing with is a problem in the grid associated with air conditioning during a peak event and what we do is we make ice at night off grid is more efficient and when it is cleaner and when it is much cheaper to produce electricity. We put in anaerobic digesters and farms so we are digesting manure primarily from dairy cows and from that manure we're creating renewable energy, we're making electricity. We represent energy efficiency technologies. They are combined heat and power systems and waste heat recovery. The first one is waste heat recovery on every industrial process, there is wasted heat, it is carbon neutral and if you put a system on it you can produce hundreds and hundreds and thousands and thousands of very clean megawatt hours. Combined heat and power is actually one power plant that produces electricity and thermal energy and this is twice as energy efficiency as normal power that you get to your house which comes off your local utility. Hydropower is our nation's largest renewable energy, it's about 60 to 75% of renewable energy in the United States, it's about 7 to 10% of our electric generation. This comes in all forms, water power technologies, conventional to pump storage, to hydro-kinetic technologies of ocean tidal and the in-stream. Solvable, portable tags have been around for decades but now the technologies are being refined, the panels are becoming more efficient and the costs for designing and installing those systems have come down dramatically over the last couple of years and they will continue to decline making solar a viable option for more and more and different kinds of electricity consumers. I work for Gridwise Alliance and we're looking at enabling technologies that will help us get renewables and energy efficiency on the grid, enable our grid to become more reliable and safer and have the ability for the consumers to make decisions about energy.