to really start the launch into the main need of the course and we'll start to talk about reactivity of the carbonyl bonds. And this is going to encompass chapter 20, but it's going to not just run through 20, but really all the way 24, chapter 44, the next six weeks. This is the main need of the course and this is also going to really be some of the intellectual height of organic chemistry. And we're going to see general themes of reactivity of carbonyl compounds and really it has to do with sort of two properties of carbonyl compounds. One is the reactivity with nucleophile, which is what we'll be focusing on today. The other property that we're going to be learning about particularly as we move through the course into I think chapters 22, 23, and 24 is that there, well maybe I should say there are reactions, I'll just look at it as reactivity. All right and the other will be reactivity as nucleophiles. What do I mean by that? Well the first one is a little bit easier to see and is where we're going to be starting today and indeed the next few lectures. And that is that the carbonyl group is electrophilic. The carbon of the carbonyl group is electrophilic and we're going to see how nucleophiles can come in and right now I'm just going to draw an arrow, not really yet representing flow of electrons to say that nucleophiles are interested in reacting with the carbonyl carbon. The second concept, reactivity as nucleophiles, we're going to see as we develop the idea of enols and enolinks, isomers, and related species to carbonyl compounds. And at that point when we start to invoke that reactivity, what we're going to learn is that the alpha carbon, alpha carbon means the one over can react as a nucleophile. And again that's not meant to represent the flow of electrons yet, just showing the position and maybe I'll go ahead and emphasize that by saying alpha carbon. So in general as you go along from a carbonyl group you'd say the carbon next to it is the alpha carbon. The carbon one beyond that is the beta carbon. One beyond that is the gamma carbon. And here we'll refer to this as the carbon yield carbon. So in its own right this diagram doesn't really say very much but it sort of lays a framework. So let's start to move from this level of abstraction to a level of bonds and structure. And let's start with a carbonyl group to be acetone or any particular carbonyl group. I'm just drawing this as a general carbonyl group.  So oxygen is more electronegative than carbon. Oxygen has a greater nuclear charge. It pulls the electron forward. In other words the carbon and oxygen double bond the bonds that comprise a sigma bond and a pi bond are while shared electrons while the covalent bond between carbon and oxygen they're not sharing equally. Those electrons spend a little more time at the more electronegative oxygen. The atom with the greater nuclear charge. And so I can represent that in terms of a partial negative charge and a partial positive charge. In other words since the electrons while spending time between oxygen and carbon spend a little more time at oxygen we shift our charge over to oxygen. There's a partial negative charge. Our carbon is a little bit deficient in charge. There's a partial positive charge. We can also represent this type of structure by resonance structures. And remember resonance structures aren't one or the other but both at the same time to varying degrees or in some cases more than one if you more than two. And so we can think of the carbonyl group as having a major resonance structure in which instead of having a double bond and having a complete octet for carbon and a complete octet for oxygen we can represent a minor resonance structure as having a single bond with a full negative charge on carbon on oxygen and a full positive charge on carbon. These structures to represent the two of them together we're thinking about we're not resonating or vibrating or oscillating between the two structures. We're mostly the one on the left and a little bit of the one on the right. This is also representing the type of electron density that you would see in the molecular orbitals for the carbonyl group. The other thing I'll point out is we're going to be focusing a lot on arrows in this course. We'll use them to think about and communicate ideas of electron flow of equilibria and of resonance. And there's different types of arrows that we use to communicate different ideas. The double arrow like this communicates resonance and communicates that it's both structures. It's not an equilibrium arrow which is two arrows pointing in the opposite direction. And it's not a flow of electrons where we draw an arrow originating at a electron and flowing at something at one section. In other words originating at the nucleophile and flowing to the electron. And that actually brings us to our next element of reactivity and that is the reaction with nucleophiles. So if you have a carbonyl group and again I'll draw it just as some generic carbonyl group not meant to represent acetone not meant to represent any particular group and it encounters some nucleophile again for now we'll just represent that nucleophile in the abstract. They can react with each other. And so I'll use a reaction arrow to show that we're going from reactants to product. The product of this reaction can be represented like so where our nucleophile has formed a bond to the carbon and we can think about how that reaction occurs by thinking about the flow of electrons from the nucleophile from the thing that has electrons to the carbonyl carbon to the carbon that wants electrons in our mind's eye we have in mind a picture where the carbonyl group is polarized and so electrons want to attack as carbon in the very back of our brain we have a picture like this is for a minor resonance structure guiding us and making us think from where the electrons want to flow. And of course we can't stop at this point because if we just left our electrons here now we would have 10 electrons around the carbon we would have more than an octet that wouldn't be possible and so electrons have to continue to flow as electrons are flowing from the nucleophile to the electrophile to the electrophilic carbon in turn electrons are flowing up onto oxygen and so when all is said and done we formed a bond between the nucleophile now represented by this line or these two electrons and we move two electrons onto oxygen and in turn put our negative charge there. As I said at that point I'm dealing with abstractions. The nucleophile here is not meant to be any particular nucleophile but now let's come maybe to something more specific and in turn this is not meant to be any particular carbonyl group but let's take a look at acetone and a nucleophile that's sort of halfway between reality and abstraction at this point and so nucleophile that I'll draw is hydride and I think I'm going to put it in quotes and the reason I'll put it in quotes is you essentially never have hydride as an entity. The very end of our discussion here I'll show you an example of an actual hydride with a hydride anion that actually doesn't react as H minus or at least doesn't react as a nucleophile but for now we'll worry about what our hydride source is in just a moment. For now just think about the abstraction of hydride and we'll have hydride reacting with acetone and so electrons are going to flow from the hydride from the lone pair to the carbonyl and again we can't stop at that point our electrons have to flow up from the double bond onto the oxygen atom and so when all is done we have an anion, it's the anion that would have been derived from isopropanol so we call it the isopropoxide anion of the broader family of what we would call alkoxide anion so if you have an anion that's derived from an alcohol that's equivalent to removing H plus from an alcohol you end up with an alkoxide anion. And a chemistry question. Oh yeah so does a nucleophile attack when the carbonyl is at its minor resonance structure or does the nucleophile cause the minor resonance? All right I'm going to toss this question which is a good one out to somebody in the class. Does the nucleophile attack when it's the minor resonance structure or does it attack? Does it attack cause the minor resonance? Or does it attack cause the minor resonance structure? Does it attack when it's the minor resonance? Okay so now we have doesn't it happen in both because it alternates. It's a hybrid yes so I didn't like the word alternate but you've got the right idea. It's not one or the other it's both resonance structures at the same time so it's not like it's waiting for the minor resonance structure they're both there at the same time. The problem is chemistry is all about models, about conceptual models. And the beautiful thing about drawings like this is they're simple we can wrap our head around. That's super, super powerful. The problem so that's the plus. The disadvantage is that these models are always incomplete so there are layers of meaning in the models. And another approach is to look at molecular orbitals and electron density but it's harder to immediately wrap our head around things the beauty about these drawings is you can scratch them in a stick on the sand or under paper and have an immediate grasp of reactivity so it's not one, not the other but both at the same time. Now the second half of your question is interesting because of course the bond forming process is one where the electrons do start to approach and as those electrons are approaching as the nucleophile is approaching the electron we're moving the other electrons continuously up onto the oxygen so in a way this is what you would call a reaction coordinate. We're going in the process from the nucleophile and electrophile being very far apart and having almost completely a double bond character in the electrophile and no bond between the nucleophile and electrophile. We're moving the nucleophile into the carbonyl group. The carbon oxygen double bond is becoming more and more like a single bond and getting weaker and weaker until finally as we've gone over that energy of the transition state and down to the product we've now formed a single bond so that's the reaction. Other questions? The questions? The stereochemistry? Ah, great question. Hang in there, question what should we be concerned with the stereochemistry? So let's start at the beginning. So the answer is yes and let's get to that point. All right, so organic chemists love to make stuff. We live and die by making new medicines, making new drugs, having reagents that cause chemical reactions and inventing new reagents and so this is a huge part of organic chemistry. It's fun because you have an idea in your mind's eye and then you test it out. So two reagents that are used as a source of this, what I would say here is abstract or hypothetical hydride anhyde is lithium aluminum hydride, two very popular and long-standing reagents, lithium aluminum hydride, sodium borahydride. And both of these reagents react as hydride with carbonyl compounds, particularly with aldehydes and ketones which is what we're going to focus on today. The structure of lithium aluminum hydride is an aluminum hydride anion or tetrahydride anion as a lithium anion. The structure of sodium borahydride is a borahydride anion, the H4 minus, LH4 minus, and a sodium cation. And you'll notice these structures are related. Boron is above aluminum in the periodic table so in many ways they have similar properties. They differ just a moment. They differ in that aluminum is more electropositive than boron. The electronegativity of hydrogen is about 2.2. The electronegativity of aluminum is about 1.6. The electronegativity of boron is about 2.0. In other words, in all of these species you have the bonds polarized to having more negative charge on hydrogen than on the metal but in the case of aluminum hydride they're even more polarized. In other words, aluminum hydride is a more reactive anion. Lithium aluminum hydride is more reactive. And you can see this in the laboratory immediately. If I take a spoonful of lithium aluminum hydride, a great powder and throw it into water, I better get back because it's going to release hydrogen with a big fizz and maybe even catch fire and if I eat it too much. It'll explode. Zodium boron hydride is a white powder that was sort of bubbled in water but won't react nearly as fast releasing hydrogen gas. And there was a question here. Yeah, I'm sorry. Would NAH also release a hydride? NAH, we're going to come to it a moment. Great question. Let's talk about some reagents and their reactivities first. So in a way, we're going to, that falls into the category of the exception and we're going to see its reactivity in a moment. All right, so let me take an organic compound. We'll take a simple compound. It's a ketone. It's a ketone with a benzene ring on one side of the carbonyl group and a CH3 on the other side. You might see people write the CH3. You might see them leave it just as a line. Both are correct ways of writing it. The IAPAC name for this compound is one phenylethanone but nobody is going to call it that. Everyone's going to call it aceto-phenone because it's one of these compounds where the common name just really dominates. So I'll write out the systematic name just as a reminder and the common name is going to predominate. And we're going to imagine treating this compound with lithium aluminum hydride. We're going to see how it reacts as hydride anion. As I said, aluminum is more electropositive than hydrogen. The bond between them is covalent but it's a polar covalent bond and it's one in which we can think of it almost as H minus or another way is we can think of the electrons as flowing from the bond between aluminum and hydrogen onto the carbonyl carbon, toward the carbonyl carbon. And remember I use an arrow from the electrons to the thing that wants electrons. I put a double, I put two little arrow heads on here as representing that we have two electrons. And for now at least I will be good at drawing my lone pairs of electrons and reminding us that we have two lone pairs and we have one more pair of electrons flow up there. And so when all is said and done with the alkoxide and at least I will be good at drawing in my hydrogen. And in addition to this, we have a lithium cation. And in addition to this, we have ALH3. And that's where I'm going to stop it at this point is at the alkoxide and I can think of it but I'll put a little bug in the back of your mind.  And reality, this lone pair can now attack one of the lone pairs, can now attack the aluminum and fulfill its octet. So technically you'll end up with an aluminum alkoxide salt. All right, so this is kind of a mechanistic way of thinking about this reaction. Let's go and think about things from a synthetic point of view. The chemists will often write equations as little recipes. Mix this with your compound and then mix in something else and then you get that. And organic chemists are very bad at writing balanced equations. Organic chemists often will just write reactants and products, question. Is there a conservation of charge? Oops, good, good point, thank you. So yes, so our lithium aluminum hydride, we have a lithium cation, an aluminum hydride anion, that's our reagent, the aluminum hydride transfers to the hydride, at the end you'll have your lithium cation, your alkoxide anion, and ALH3, which as I said, will typically bond to oxygen. Also, typically that undergoes further reaction with additional ketones. So often when you're doing the reaction in the laboratory, you don't mix one mole of ketone and one mole of lithium aluminum hydride, but you might use two moles of ketone or even three moles of ketone and one mole of lithium. So let me write a reaction as a synthetic organic chemist would. So now I'll be a little bit sloppier in the sense that I'm not going to write in my lone pairs of electrons. We're thinking more like a synthetic organic chemist, not even going to write in my metal group. It's implicit over here. And so step one is treatment with lithium aluminum hydride. I'll write it as LIALH4, but sometimes you'll see and abbreviate it as LAH, lithium aluminum hydride. And then I'll write in a second step in this recipe. And I'll write in the step H3O plus or your textbook writes H2O, and I'll tell you about that in just a second. And then I'll probably also indicate the solvent that I would use to carry out this reaction. And typically I would carry out the lithium aluminum hydride reduction reaction in THF or in diethyl ether. So this constitutes a little recipe. It says take some benzo phenol, put it in a flask with some THF or some ether, throw in some lithium aluminum hydride, and then after a while after the reaction is done, throw in some acid or some water.  We have aqueous hydrochloric acid which of course is H3O plus and CO minus. We have aqueous sulfuric or concentrated sulfuric acid which you can add to the water to make H3O plus and bisulfate N9 HSO4 minus. So that's a little bit of a short hand for adding an acid that you would get a strong mineral acid like HSO4. Now I think we call this step here the workup. So I'll just write solvent and I'll just write workup here. Honestly, this particular one you could do with either aqueous acid or with water. Aluminum salts in water under the warm condition can form tremendous gelatinous things. You've all had lab, you've all shaken a sept funnel. You may have even encountered an emulsion. Who's encountered an emulsion?  The advantage of throwing in a ton of acid is it dissolves all of the aluminum salts and gets rid of the emulsion. You can also add water in just the right way, a little bit of water, a little bit of sodium hydroxide, a little bit of sodium sulfate which makes your aluminum instead of gelatinous, makes it granular. So either of those work for a workup and you'll see things written both ways. The main thing, of course, is that until we add something that provides a proton, whether it's acid, H3O plus aqueous HCl or whether it's water, we have an alkoxide anion. But after the workup, you isolate your product, the almolyl. And as I said, organic chemists are typically very bad about balancing equations. So typically, this becomes a little recipe. And as I said, I'll just write it explicitly. Our workup ends up taking our alkoxide anion of the alkoxide anion plus H3O plus, plus hydroxide anion or plus water under the right circumstances. And electrons flow from the alkoxide to the source of protons and electrons flow from the source, from the hydrogen oxygen bond, onto the oxygen. And we call this step the workup. What are the questions or thoughts at this point? Ah, does it always make a secondary alcohol? Good question. If we had an aldehyde, we would get a primary alcohol. Of course, you couldn't have, you couldn't make a tertiary of alcohol with hydride nucleophile because by definition, hydride is going to add in a hydride. Next class, we'll learn about Brignard reagents and Herbanolythium reagents that instead of adding a quote-unquote H-minus can add an alkyl group like quote-unquote metal-minus, and you'll see how to make a tertiary of alcohol. All right, there's a concept that really is useful in permeating your thinking. And that concept is oxidation state. And I introduced it last time when I was talking about the carboxylic acid family. And I said in the carboxylic acid family, the oxidation state of an alcohol is or the oxidation state of the carbon is plus three. In a ketone family, the oxidation state is plus two. If you remember in calculating oxidation state from general chemistry, you play a game where you divide up the electrons giving them to the more electronegative atom and then saying, okay, what's the net charge on the atom? If you have a carbon bound to another carbon, you divide them equally. So in a ketone, the oxidation state is plus two. All right, ketone here in our product, in our particular alcohol that we've generated, our secondary alcohol oxidation state is zero. So if you notice by going from an oxidation state of plus two to an oxidation state of zero, we have undergone a reduction reaction and the chemical that's done it, then, our lithium aluminum hydride is the chemical or the reagent that carries out the reduction reaction. And there are many different reducing agents. I drew another one. I drew sodium borohydride and let's talk about that. And I'll give you an example. It's the very astute gentleman asked the question about aldehydes, let's take, or primary alcohols. Let's go ahead and take an example of reduction of an aldehyde to a primary alcohol. And so we'll take Benz aldehyde. Benz aldehyde is a very nice smelling compound that kind of smells of cherries. It's sort of the flavor of cherry coater, artificial cherry flavor. If you take, for example, sodium borohydride, the reaction would work with lithium aluminum hydride but I'd like to introduce you to other common reducing agents. And in this case, you can actually run the reaction in a cell that's like methanol or ethanol. As I said, sodium borohydride reacts only slowly with water if I threw, if I tried to run a lithium aluminum hydride reaction in methanol just like water, it's a source of hydroxylic protons. If I tried to run a lithium aluminum hydride reaction in methanol, I'd be rewarded by the whole thing that best spatter would be in the face and worse had to be fired. A reaction here, Benzalethylhole. And we can think of this reaction occurring very much like the other reaction has occurred. So here's our aldehyde, here's our borohydride anion. Hydrogen bond is polarized. It's a polar covalent bond with more electron density on the hydrogen. And so for a hydride anion I can transfer a hydride and it has a nucleophile to the carbonyl group. And again, we pick up our electrons onto oxygen, oxide anion, inserting a little bit loosely because BH3 doesn't have a complete octet. And so typically it's going to form a bond with oxygen reversibly, but we can think about it. Now the nice thing about running this reaction in a hydroxylic solvent is you've got this huge, huge excess of methanol. And so methanol can protonate the alkoxide anion. So here we have our alkoxide anion. We're in a ton of from the oxygen of the alkoxide anion to the proton of methanol. We put electrons back onto the oxygen and after all is said and done in this equilibrium reaction now driven by the mass action of having so much methanol in it. And our alcohol in methoxide anion. The methoxide would be more happy without the H or without the H. Great question. Would the methoxide be more happy without the H or with the H? So in general if you want to sort of keep one thing in mind, the basic rule would be all alcohols have pretty similar acidity. Water I said to PK was 15.7. That's sort of at one extreme methanol. It's about 16 ethanol maybe pushing towards 17, 16 or 17 terbutanol toward 18. Benzyl alcohol is a little bit more acidic inductively. But the main point here is we've got a ton of methanol. Your methanol is 20 or so molar and you've got one molar of compound. So you've got this huge excess of methanol grinding this equilibrium to the right. And then you're going to do an aqueous workup in the end that's going to extract your compound into an organic cell. So you're right. It is an equilibrium. In this particular case it's okay that it's an equilibrium. But that equilibrium, remember I was talking about PK last time and I said the thing that we really want to be able to focus on in organic chemists, it does need equilibrium like way to the left, way to the right, kind of in the middle or maybe a little more to the left or a little more to the right. That's how we think about things. And you're right. This equilibrium lies kind of sort of in the middle. Oh, ah. Well, if you tried to run a lithium-aluminum hydride reaction in methanol, the lithium-aluminum hydride would probably first react with the methanol. And as I said, they hydrate it so vigorously and so rapidly that it would blow up in your face. So it would definitely react with the methanol. It might also react with the ketone, but I'm not going to try the experiment in the laboratory and see at the end when I wash my face off whether I had any of these ketones. So in this case, in this case we started with benzaldehyde and the oxidation state of benzaldehyde is plus one. By the time we've gone to benzal alcohol, again, it's a reduction reaction. The oxidation state is minus one. Now, this is important in thinking about families because remember I said carboxylic acids and the whole carboxylic acid families, esters, amides, nitriels, all that entire family is plus one. They are more oxidized than aldehydes and then aldehydes are more oxidized than primary alcohols. And you'll notice they go in twos and this is pretty common in organic chemistry. As you change oxidation states, almost invariably, you end up going into some organic chemistry. It's important to sort of keep this in the back of your mind is it helps you focus your thinking. When you change from a carboxylic acid to an ester through a chemical reaction, there's no change in oxidation state. You wouldn't think about using an oxidizing agent or reducing reagent to affect that change. You're changing the same oxidation state. But when you're changing from a ketone or an ester or an aldehyde to an alcohol, then you're changing oxidation state and you think about using a reducing agent. If you're changing from an alcohol to a ketone or an aldehyde or an acid, you would think about using an oxidizing agent. There are a ton of hydride reducing agents. Your textbook has given you some. I'll show you a few others. The general principle, the overarching principle of hydride reducing agents is that you have a metal hydrogen bond, metal broadly defined, polar covalent bond where you have M with a partial positive charge and hydride with a partial negative charge. By broadly defined, I mean that boron is kind of a metal or a metalloid, aluminum is a metal and there are many others. So the general principle, as I said, with lithium aluminum hydride technically after that first mole of hydride is transferred, technically what happens is the ALH3 reacts with the alkoxide and now this intermediate can transfer again hydride anion to another carbonyl group which is why you may only use one mole of lithium aluminum hydride for several moles, for two moles or three moles, up to four moles, although typically you wouldn't use it of your electrophile, of your carbonyl group. Your textbook gives an extreme example of this where you transform or you preform the reagent with four, with three tert butoxy groups on aluminum and this is a less reactive hydride source. There are two reasons for this. One reason why once you start to put alkoxide on the aluminum, it's less reactive is that the oxygen is electronegative and it's pulling electron density away so there's less of a partial minus charge on hydride. The bond is less polarized. Another reason is sterics, the tert-fuel group is very big and so that big set of tert-fuel groups gets around the way of this. So only the very most reactive carbonyl compounds react with a tetra tritrefuse-toxial aluminum hydride reagent. Even metals that don't have a full octet can react as a hydride source. Your textbook mentions and we will talk more about in a moment or later lithium, a diasecule aluminum hydride, abbreviated dival H or sometimes just dival, you will see it. And again, you have a polarized metal bond.  I'll just show one other reagent, sodium cyanoborohydride. It's another hydride reagent that's less cyanobroops or electron withdrawing and so sodium cyanoborohydride is less reactive than sodium borohydride. There's a big alphabet soup of different reagents out there but you'll notice that the general theme in all of these reagents is that a metal is bonding the hydrogen. So the various students' question was asked about sodium hydride and that sort of is the oddball exception. Sodium hydride, NAH, actually reacts as a strong base not as a reducing agent. All of the reasons for this, all of the reagents I showed over there and the sodium borohydride and the lithium aluminum hydride have covalent bonds between metals and hydride. Sodium is even more electropositive than aluminum. Its electronegativity is about .9 and so the sodium hydride is actually an ionic compound and it's pretty darn insoluble in organic solvents. As a result, you never really have a chance to have soluble hydride and it doesn't get into and react as a nucleophile plus because the bond is very ionic and because hydrogen is relatively electropositive compared to say chloride anion, sodium hydride is a very strong base and so in general, if you take sodium hydride with almost any source of protons, water or say methanol, it reacts and so if I throw sodium hydride into say methanol, it reacts to form sodium methoxide and hydrogen gas. Remember I was talking about acidities before and saying well you don't typically calculate things but you'll keep in mind where an equilibrium lies based on the difference in pKa's. Hydrogen has a pKa, so this is an acid base reaction. Hydride anion reacts with methanol to give methoxide anion. I've just shown it as NaOCH3 but of course that's Na plus OCH3 minus an ionic compound plus hydrogen gas. So this is an acid base reaction. The methanol is an acid pKa about 16 or 17. The hydrogen is an acid on this side of the equation. Its pKa is about 35. It's a very weak acid whereas methanol is just a weak acid so that reaction, I won't even write it as an equilibrium. That reaction lies way, way, way to the right. pKa of 35, pKa of 16, difference of 19. If I were to write an equilibrium constant it would be 10 to the 19th, just massively on the right. So that reaction ends up reacting as a base. For some questions, the sodium hydride react violently at water, absolutely. If you get water on it you see a beautiful bright orange flame and the big danger, if you were to take a scoop of it and throw it in water you'd get a big flash of fire. But the big danger in the laboratory is when you're weighing it out you spill a teeny little bit and later on you're cleaning up and splattering acetone and splattering water around and at that moment when the water hits an acetone is splattered around all the acetone and all the solvent goes up in fire. So when I work with sodium hydride what I'll generally do is get a wad of wet paper towels and wipe down my work area and I might see a little flash of orange and then flash of orange under the big wet wad of paper towels doesn't do any harm and it prevents must be from having a fire over and lighting lots of acetone over fire. How do you find oxidation state numbers? Okay, great question. Oxidation state, state two examples here will start with an extreme example, carbon dioxide and methane start with carbon dioxide. Carbon has four nuclear charges, we have eight electrons but we're going to play a game here, the game is that we give all those electrons with the electron to oxygen, we play with all those electrons to oxygen and we've none for carbon because oxygen's more electronegative. Because we have a net four nuclear charge, the oxidation state is plus four. There's more electronegative than hydrogen so we play the same game but now we give our electrons to carbon so we have plus four in the nuclear charge minus eight before electrons and our net oxidation state is negative. Less case. Sorry Professor, wouldn't the oxygen also have a negative charge? Yes, the oxygen, I wasn't counting on the oxygen. The oxidation state of oxygen is negative two here because you have six nuclear charge minus eight electrons and the oxidation state of hydrogen here is plus one. I'm only counting for carbon. So why does carbon go from plus four to minus eight? I don't get it. Why this, no, no, no, you take the nuclear charge minus the number of electrons so you take your nuclear charge and calculating oxidation state plus for the outer valence plus four, right, you have the one S which you don't count in two of the nucleons, two of the carbon ions, right. So you count carbon spore across in the periodic table so carbon atom is carbon nucleus plus four electrons but now in calculating oxidation state in carbon to oxide we're taking all those electrons away in methane we're giving it four more electrons. Okay. And in ethanol, let's say our last example, ethanol to play the same game here will divide up our electrons in ethanol and for the metals we share and share alike and so for ethanol our carbon is, so this is our primary alcohol, our carbon brings for nuclear charges, we take away five electrons and we're at negative one oxidation state. Now, let me tell you honestly, I am not generally calculating oxidation states in my head but it definitely is a romantic penance permeates my thinking. In fact, I think in broad terms, I think acid oxidation state, aldehyde oxidation state, primary alcohol oxidation state and I realize well ketones are shifted by one, secondary alcohols are shifted by one but they go in care. So when I'm thinking about stuff it's definitely not this calculation, this is just the underpinnings of my thinking. When I think about a reaction of say an alkene and a hydrogen I think carbon carbon shovel bond now gets replaced by carbon carbon single bond plus two carbons bound to hydrogen that's taking my oxidation state to be carbon down by one or taking me down by next to a oxidation state. When I think about say forming a general diol from an alcohol I think oh I'm going up and when I think about hydrating alcohol I realize one carbon's going down, hydrating an alkene to an alcohol, one carbon is going down, the other is going up, they balance out. Sorry, question so for the soft side one why does the CO have why do you like carbon? Why does the CO, here? Sorry the carbon, how come the carbon? Bookkeeping, when you have a carbon carbon bond you divide equally you give one to each carbon in bookkeeping for oxidation state. All right so that's what permeates my thinking on oxidation state. The biggies become the acids family, the aldehyde family, the alcohol family and then the ketone and secondary alcohol. So I want to talk a little bit about reactivity toward nucleophile, toward hydride and other nucleophiles in a very good generalization. Again there are always exceptions to generalization but a very good generalization is the aldehyde's active in ketones and ketones are more reactive toward nucleophiles than carboxylic acids and esters. One way to think about this, so this means for example if I were to mix a mole of sodium borohydride with a mole of an aldehyde, a mole of a ketone and a mole of an ester, I would expect the aldehyde to react first. In other words if I monitored the reaction by thin layer chromatography, the first species I would expect to disappear would be the aldehyde. So if I wanted to give a particular example just so I don't put this in the abstract, let's compare acetaldehyde, acetone and let's just say methylacetate CH3, so why can we think of this, this way? Well think about our resonance structures. So you think about the carbonyl resonance structure and you'd say okay we have two resonance structures that we need to worry about in general for a carbonyl group. One resonance structure, the major resonance structure in which the carbonyl has a complete octet and the minor resonance structure in which we have separation of charge and the carbonyl doesn't have a complete octet. Now in the case of acetone we have two methyl groups here. Those methyl groups are stabilizing by electron donation. About carbocations you learned about hyperconjugation. You learned that a tert-butyl carbocation is more stable than a isopropyl carbocation which is more stable than an ethyl carbocation. In other words a tertiary carbocation which has three alkyl groups donating electrons by hyperconjugation feels less pain from that positive charge than a secondary carbocation and primary carbocation and it's the same principle over here. When you have alkyl groups on both sides of the carbonyl that carbonyl is less electrophilic. It is more stabilized by electron donation. When you have an aldehyde like acid aldehyde it's more reactive because you have only one alkyl group stabilizing and if you have the one aldehyde with no alkyl groups from aldehyde it is extremely reactive because there is absolutely no stabilization of the work. In the case of an ester you get a little bit of extra stabilization here because you can write a second resonance structure and I'll just go ahead and complete my lone pairs here. You can write a second resonance structure like so that provides an extra special stabilization of your positive charge of the carbons. You get one additional resonance structure. I saw a question. The question was if you have an aldehyde with, so the question was very clever. If you have an aldehyde could you have a high drive ship? And the answer is that the partial positive charge is not enough on its own to introduce a high drive ship. However, there are certain reactions. For example, the pinnacle rearrangement where you can go ahead, actually not the pinnacle but there is another rearrangement where you can go ahead and push a high drive ship once you've protonated the carbonyl. So the short answer is not for an aldehyde per se but your thinking is actually self. Another question. Well, I always like to think of it just, so the question is can I explain how it's stabilized by electron donation? I like to think of the methyl groups as just electron donating. In the case of a carbocation I really would write a non, remember the non bond resonance structures where you actually write a double bond between the carbons and then you write H plus. It's that exact same thinking. Oh, I lose those so far as the right sense. It basically think of it as each of these CH bonds, remember the hydrogen is more electropositive than carbon so each of these CH bonds puts more electron density on the carbon which inductively donates it in. I'm going to take one last question and then I want to wrap up a couple of concepts that came up. Okay, well of course the S there would it be better if the positive charge is on the carbon instead of the oxygen? All different resonance structures. Ah, your question is this a better resonance structure than this and the answer is no and the reason the answer is no in terms of contribution is we have two competing ideas. We have the idea that atoms want to have complete octets and the idea that in general when there's a choice put the electrons on the, put the positive charge on the more electropositive the less electronegative atom. But the one that wins out in terms of being more important is octet. And so in an S there are three different contributing resonance structures. That resonance structure is a little bit more important than the other resonance structure but they all contribute, they all stay home. All right, I want to bring up a concept that was asked about at the beginning and I promised to get to it at the end and that was the concept of stereochemistry about a reduction reaction. When we for example take our benzo phenome treated with lithium aluminum hydride and then we do a work up with water or aqueous acid as I said it's okay to use either and I write this alcohol as our product. Even though I have written that molecule flat there is a stereogenic center in it. The carbon is a stereogenic center. There are four different substituents attached to that carbon. Doesn't matter whether I draw it or don't draw it, it is.  We can have the other enabler and unless I do something special to only get one, unless I bring to bear some source of chirality I get both enantiomers. It's chirality to make chirality. If I take an achiral reducing agent like lithium aluminum hydride or sodium borohydride and I take an achiral ketone I will get both enantiomers in equal amounts as the racinates. All of the proteins in your body, all of the amino acids in your body with the exception of glycine, all of the sugars in your body, all of the nucleic acids in your body, all of the lipids in your body are chiral. And in general, chiral molecules of one-handedness interact in a different fashion than the other.  And for that reason, there is a tremendous interest in synthesizing chiral molecules of just one chirality as drugs and for many other purposes because often the biological activity of one enantiomer is different than that of the other. In medicine, one may have a desired effect, the other may be toxic. That's one of the reasons why many of the form babies were born due to polyamide where the enantiomer, which is given to combat nausea and pregnancy in the 60s, the enantiomer induced both effects. So in this reaction, if we take in your textbook, your textbook focuses on one particular reagent called the CBS reagent. In part because you're the author of your textbook got her PhD with Nobel Prize winner E.J. Corey who invented this reagent. But in general, there have been many sources of chiral hydride reagents. And the general goal is instead of making one enantiomer, and the other in equal amounts, you get just one enantiomer. And your textbook develops the idea of which one you get at this point in the thinking. It's not so important. But realize that if you're a man with a ketone and I came forward with this hand bearing a hydride, I would have transferred that hydride to the pump. And if I had come forward with this hand bearing a hydride, I would have transferred it to the back of your hand. And just in the same way, we can bring in the hydride from one face of the carbonyl, from the front face of the carbonyl to end up with the hydrogen pointing outward to end up with the R stereochemistry or with the hydrogen coming from the back face of the carbonyl in this case to end up with the S stereochemistry. Now, I've written just one enantiomer. That's not quite true. It's very, very hard to get just one enantiomer. The molecules in your body, the enzymes, are so big and so good at engulfing substrate molecules that they're very good at generating just one enantiomer. In general, chemical reagents generate mostly one enantiomer. 99% is very good or 99.5% is very good. There's a magic number that Johnny knows for kilocalories per mole. And what is that number? 1.36 take-outs per mole at ambient temperature, about 1.4 kilocalories per mole that corresponds to a 10 to 1 difference in rate constant or a 10 to 1 difference in equilibrium constant. A parallel reagent that fits with 2.5 kilocalories or 2.7 kilocalories better on one face than another can select 99 times as good. Now, I want to finish up with one last concept here. And what your textbook is talking about is really the big ideas here. They're getting, and this is one of the problems I have with your textbook is sometimes, sometimes in trying to present the big ideas, you end up getting lost in the little pieces and never seeing the bars on the trees. So I'm just going to present one sort of more big idea that ties into the same thing. Imagine for a moment now, and this is in a way, a little easier to wrap your head around than an anti-immers and it doesn't really involve moving hands to demonstrate it. Imagine for a moment that we have tert-butyl cyclohexanone and the tert-butyl group is on one side. I've drawn it as a wedge. I've drawn it coming out. And we treat this with sodium borohydride. Now, the hydride can add either from the front face or from the back face.   We call the relationship, the stereochemical relationship between those two molecules. Diastereomers. And now, even in the absence of any sort of chiral reducing agent, we don't get equal amounts because these two molecules aren't equal. We happen to get the 80 to 20 mixture. The mixture ratio isn't so important, but it's a little bit easier to see if we go ahead and we look at drawings. So the tert-butyl group is very big.   And so here's our cyclohexanone. And now, we have two ways that hydride can come in. Hydride can come in from the top or hydride can come in from the bottom. If hydride comes in from the top, end up with this diastereomer, the transdiastereomer. And if hydride comes in from the bottom, now we end up with the axioloate, we end up with the six diastereomers, the minor diastereomer. And the last thing I'll point out is organic chemists are control frees. When we synthesize molecules, we want to have absolute control of what we make. So naturally, for the same reason I talked about enantiomers, you want to make the right enantiomer of the drug. You want to make the right diastereomer than one that you need. And so naturally, if nature did an 80-20 mixture of cis and trans, of trans and cis diastereomers, organic chemists have come up with ways to flip it and either get all of the cis or all of the trans. I'll see you next one and have a good weekend.


Hey, hello, buddies. I have a featured seller video for you guys. I kind of got away from doing these and I am back So I posted in my Facebook group requesting that three people message me if they'd like to be featured I am gonna feature Bill Stoner. He has a great store.  These are items you can be on the lookout for at thrift sales garage sales Places like that. I said thrift sales. I mean thrift stores. All right, you guys. Let's get started Thanks Let's get started as I go into his store and I look at his solds and I find some of his Higher solds or items that I think are interesting will help you guys learn. So I want to thank Stoner for doing this Let me pull up the screen share here and And I want to show you guys he does have a YouTube channel. It's a reseller channel So definitely go that out is Billner. I will also link that in the description of the video His store is your deal auctions. So that's his eBay store, which I will also link down below so you guys basically this way for other sellers to Help you guys learn but it also gives you the opportunity to check out their YouTube channel if they have one or Check out their eBay store. So definitely go down that link and go in and see what else they're selling Maybe check out their solds. So definitely show your support that way because it takes them time to get me this information And I really really appreciate it. All right, let's get started here with some bolos All right, first item is Maul Madness and I have talked about this one before now the cool thing about this one is It's not complete. So he says missing some pieces He paid $1 at the Goodwill and sold it for $64 and 48 cents plus Shipping and like he's saying here some that are complete and in good condition can go for over a hundred So there are different Maul Madness so make sure you look it up if you find one. They're not all bolos But if you find this one, definitely definitely grab it All right, the next item we have Precious moments nativity. I find that Nativity items just sell really well. I have a tendency to pick them up. So when I saw this I was like I would have picked this up for sure so he This was part of a huge collection that he bought for $160 he said there are several hundred pieces He said he put up a video about it on his channel and he sold this for $80 with free shipping So if you want to learn more about these precious moments, definitely go check out that video All right, this risk it looks like it's a board game. I believe let me see what category it's under Maybe Yeah, so it's a board game and it looks like it's sealed in the brand new packaging here So I do have a video on board games that are Bolo's. It's a Bolo category Video so you guys can definitely go check that out my youtube channel He says he got this for three dollars at an auction and it sold for a hundred and ten dollars plus shipping So definitely be on the lookout. It says risk God storm the game of earthly domination and beyond sealed guys Think I'd pick up any game that was sealed that was vintage. I don't know if this is vintage or discid you know what I mean Okay, check out these high tops. These are like super high tops Nike Air Force one women size 8x xv. I'm sure that's a number. I don't know what number it is Sorry, but anyway, he got it from a storage unit clean out for free zero dollars and he sold it for 60 plus shipping The next item is this pipka Santa's toy Santa memories of Christmas. So it's a display. Here's the bottom. It's 319 out of 3200 So pipka pipka not one I've heard of but I'm definitely going to be looking for it Came from a box of Christmas items from an auction He paid five dollars for it and he sold this for fifty five dollars plus shipping He said this was broken by the post office. He had to file a claim. So that's unfortunate. It arrived at the Fires home broken unfortunately, man, that's a bummer. That would be a hard piece to ship and you know They're not always real friendly with some of the packages Okay, guys, this is a 1997 Sabrina the Teenage Witch. It's a Gosh, I'm not sure if I'm saying this right Gija G G Giga Giga GIGA pet All right, this was from a storage unit clean out another one from the key ring Sold for 68 dollars and 40 cents with free shipping. I also had to clean and test all of these and stalled new batteries So when he says all of these I'm going to show you Here shortly another one that sold for big money So very very cool So this is a cramps Vintage punk rock band t-shirt size small. There's your tag and It's kind of crazy looking I don't know what cramps is maybe it's a punk rock band. It's a punk rock band I just answered my own question This he got from a storage unit clean out and he sold it for 40 dollars with free shipping The next item is this hand carved fist. Check it out Cool is that he paid three dollars at an auction and he sold it for 40 dollars plus shipping Never seen anything like that. Very cool The next item he sold are these Pez dispensers. I also have a video on Pez dispensers It's a Bolo category video it kind of tells you what to look for when you're looking at Pez dispensers because They are not all created equally some can go for like over a thousand dollars And then others are bread and butter. He sold this lot for Let's see. I'm sorry. Let's see what he paid for it Vintage Pez paid four dollars for a large box full at an auction This saw a lot sold on a seven day auction for seventy one dollars free shipping And he said I'm editing a video Pez should be up soon. So definitely check out his channel and look for that video also Mine is up now. If you guys want to check that out But he may have different information than me. So I did mine was uh I'm not a Pez dispenser I don't know tons about it. I had to do some research for the video. So he may know more than me for sure All right. The next item is this health master blender. It's the replacement with the tamper lid and he got this My order got a little bit out of Okay, here we go paid five dollars at an auction motor did not work correctly. So sold as parts sold for 22 plus shipping This was a large item. So shipping was so much Was as much as it sold for so he ended up taking a lower offer because The shipping was so high for the buyer The next item department 56 Christmas in the city church came from An auction he paid three dollars for it and it sold for 49 dollars and 99 cents and the buyer paid shipping The next item is this graphing calculator and it looks like it's tested and working with the cover and I sold one of these that I got out of a Mystery box from a giveaway that I won from harry tornado. It's in one of my videos But mine was pink and it did not have the cover and it was still a bolo without the cover just fyi So he paid three dollars at an auction for this and sold it for 60 dollars free shipping The next item he sold is this cowboy It's a straight razor and I don't know what the is that just like a case for it. Hmm Partial box i'm not really sure exactly it says no nicks very sharp So it's a razor. Ooh Check that out Check that out. Okay, so he got this at an auction for three bucks and he sold it for 45 dollars free shipping The next item is this 1945. It's a ts 13 E radio handset radio And I first saw this I thought it was like a cord for one of those old telephones I'm like, oh cool. He just sold like the top of the phone But now i'm reading it and it's not what I thought it was but this is still cool And he got this What is this thing called? Sorry guys Um, maybe I missed this one just a second. I'm so sorry Okay, here it is bought two of these in a lot for four dollars at an auction sold for 25 dollars plus shipping Then okay, that's what I was telling you about. He must have got a bunch of these this one is rug rats and it's a Gija Giga I don't know but it's rug rats nickelodeon and this one He uh was the storage clean out also he sold it for 40 with free shipping He said I found a bunch of different ones all on a big key chain in a box at a storage unit. Oh my goodness I have some I think he sold one. I think I have it. I'm gonna show you here in a minute Like the one I sold that is definitely a bow low Okay, these nike air force one valentine's day red pink heart shoes These he paid three dollars for it an auction sold on a seven day auction for 169 dollars and 48 cents plus shipping He said this was the second time I ran the auction the first time they were at a of Zero or there were a lot of zero feedback bidders and the winning bidder was in france and didn't pay the first time They sold for 355 dollars So 355 dollars, but non paying buyer they're paid Okay, these are vintage Levi's for gals. So they're big e pants, but they're um a size 24 26 so I believe that's like a girl's size 26, but they are big e vintage. How cool is that? all right These came from a storage unit clean out So he paid zero dollars for it and sold for a best offer of 50 dollars free shipping So maybe I should call this video. He got it free Because he got so many items free. It's awesome Um Okay, nike II Nike Air jordan air force one. Okay These came from a storage unit clean out guess how much free And he sold them for 84 dollars free shipping Okay, so this is an escort solo cordless radar and laser detector And he paid three dollars at an auction. This was from the police in pound And he sold it for 160 dollars free shipping. So That's the type of auction. I've never been to that would be cool All right, this sony camera. So it is a camcorder not camera camcorder with remote and cables And he got this At the salvation dollars and he sold it for 139 dollars and 48 cents And I guess I didn't pull the other one up. I'm trying to think of what the other brand was It's like tamagotchi or something like that. I know he sold one But yeah, definitely be on the lookout for those. Okay, so here is his store your deal auctions And his youtube channel is just his name bill stoner And definitely go check out his I was trying to think What was the he said he did one on the precious moments Don't see it through there. You might have to go and actually uh search for it So definitely go check that out again. The links will be down in the description of the video Thank you for being here. Thank you for watching There should be some other videos that are going to pop up on both sides If you haven't subscribed be sure to subscribe be sure to check out the description of the video like comment share and subscribe Thanks for watching


So, this is a regular meeting of the new board for the town of Berlin. We have one application before tonight. I'm going to start with the productions however, since everybody's wearing a mask. My far left is Tour Delsen. Paulie McMurtry. Paulie McMurtry, good board. It's okay, it's a long day. I'm the zoning administrator. Carl DeWiesel, member of the board. And myself, I'm Bob Wernick. I'm the chair of the board. If you all would introduce yourself, I'll start with you. On the left, Bernie. Bernie Shannette, representing the architectural control committee, review the control committee, practice firms association. I'm Jane Bartram. And a butter of the property being discussed. Marty Bligerstead on a butter as well. Meg Grubos on the architectural control committee for a practice firm. I'm David Grubos, the president of the practice firms association. Lewis Gritzer on a butter of 69.3. Okay, and who do we have on? Okay. So I'm going to introduce your crew. Trish. There I'm a little slow on that. So it's a, we've got Joel Baker here. And myself. And I'm going to close myself. Yeah. I'm sorry, Trish Sawyer. I'm the realtor. Working with Joe. Okay, thank you. And Joel's the property owner. I'll let him speak on his for himself. Hi, everybody. Yeah. No, nobody's been sworn in to speak yet. So. All right. Catherine, can you introduce yourself? Catherine Lagerstead property of butter at 99 point Ridge Road. Kathleen, can you introduce yourself? This is Catherine Lagerstead 99 point Ridge Road. Yeah. Kathleen's my wife. She doesn't. 69 point Ridge. Kathleen McDonald. Okay. So. Before I begin anything tonight, I want to swear but again, because of your testimony, but I think before I do that, I'm going to ask, is anybody here requesting party status on this application? Party status is required. If you want to, you can testify, but if you want to appeal or be involved in the decision, you need to have party status. Party status is awarded to what? I think there's five different categories. Should I read them to you? Most common is in the body. Most common is butter. But one of the most common is butters. Or, particularly in the immediate neighborhood. So that's the most common that people apply under. So who wishes to have party status on this matter before the war tonight? Besides the applicant obviously. No one? Okay. Hey, Christine. Christine's our recording secretary. So I'll start by swearing everybody in. It tends to get testimony before the sport tonight. Please raise your right hand. Swear to tell the truth. Nothing but truth. And as before the sport tonight on the penalties of perjury. I do. I do. Thank you. So. We start by asking the applicant to describe the nature of their application. Okay. Well, I bought this lot along with four others in the neighborhood. I think in 1995. And the intent was to build or sell on these lots. And for whatever reason, I was a builder at the time. More or less retired at this point. But for whatever reason, I never got around to building any houses. On these lots myself. So we sold four of them. And some of them, I believe were built on some or not. But we hung on to lot 35. For no particular reason. I mean, it was. In my case, it was kind of an out of sight, out of mind thing. And. It's kind of, it's come back to the surface in this environment. You know, I'm older. I don't need it. I'm not going to build on it. I'm not going to sell it. So. That's what's motivated. Myself and Trish to kind of pursue this. So. You know, my belief when I bought it, it was a plan residential development or a planned unit development, whatever. I thought at that point that. You know, all the permitting was pretty much established. And so. Nowhere was there any reference to this slot being any different than any other lot. And so. Apparently we need a curb cut. Which is fine. So that's why we're here. Yeah, I actually, my apologies. I failed to. Really read what this application is that is before tonight. It's just so we know what we're looking at here tonight. In application by Mr Baker for a request under section. 3203 B for B. To reduce the spacing of a new curb cut. When it is not physically feasible to achieve required spacing on the applicants. Obtaining an access permit in the town. So this is actually asking for permission to reduce distance between care cuts. And this between curb cuts is governed by our regulations. Largely by reference to. All the state standards. For transportation. And that is. B71 B71 which is now B71 B. B71 a. Bylaws speaks to B71 was now by law B71 a which is residential drives. And that basically speaks to distance between. Curbs. In case of 100. What is the speed limit on that world you know Tom. 25. You should know for sure. That's 155. 155 feet between curb cuts. Is what's recommended by the. B71. A. So. And that's not directly it actually makes reference to. States. Access management program guidelines. Which you have to sort of read those to get why we're here. Yes Tom. Mr. Chair. Context to this discussion tonight. Please. This I spoke to. So early on in this process. And. My understanding back in 1995 the town of Berlin did not require curb cuts. And these blocks were developed without. In effect seeking a perfect permit. And that's why we're here now that maybe answers Mr. Baker's question. Mr. Baker's question. Why I thought all the permitting was in hand. We bought a lot but. That's my understanding is that back then. Perpet permits were not required. They are required today. And so. I spoke to. Miss Sawyer. And. And suggested that. Because. Perpet permits are issued by the Berlin select board. That. Her most expedient way through the permitting process would. Would be to. To go visit the select board and request a curve cut. The. The select board was. Notified in advance of our regulations and they said. They really wanted the DRB to weigh in on it. On that. So they they have put off their decision on the curve cut. My sense is it's again my sense is. If. If. The DRB. The grant. A waiver under under this section. That the select board was likely granted. One thing. Yes, go ahead please. As I understand it. You know, when a planned residential or planned unit development is put together. The intent is to. Intensify. The development patterns. In other words. Get a higher density. And to that end. Your standard dimensional. Regulations are. Not really considered. In other words, the setbacks are less. These lot sizes are less. Everything is. You know, I think it's a little bit. I think to be a little bit condensed. And you know, there's. It's a dead end road to a cul-de-sac and. It's not a 50 mile an hour drive by. Thank you. Yeah, we were talking here about a provision under the. Commercial drives and then. Residential drives and say. Must be new curb cut. So. Okay. New curve because it was separated by existing approved curb cut. The same side. The road from any intersection that is specified by B 71. B 71 a. Except that they'll be. Reboard may. And you probably all have read this. Reduce the spacing. If it's not physically possible to otherwise. So obviously there's what's the right away. 20 foot width. It's not a, it's not technically a right away so much as just the dimension of the property. Okay. Yeah. Very good. Questions by members of the board. What is the distance? Yeah. What will the distance be. This is would be. I'm sorry. What was the question? What would the distance to the nearest driveway being from your driveway? You know, I just have. I have the lot boundaries in front of me on a map, but I don't know exactly where the. Where the driveways are located. I mean. There's a drive next to me or a lot next to me lot 44. The total width is 112 feet. So obviously that's not going to be 155 feet from anywhere. The lot on the other side lot 33. The total width appears to be. Approximately 130 feet.  Well, it appears that. The driver will be adjacent to the. Is it the one driver? Yes, it would be a matter of feet. Yeah. It would be a matter of probably less than 20 feet. Right. So. So this. This lot was approved back in whenever the. Was approved the shape of the lot and all. Correct. In 1988. Okay. The question by board members. Questions or comments by. People who have asked to be. Involved tonight. Our architectural control committee has submitted a letter. I believe it's October 28th. Which sort of describes the. Concerns that we have regarding development of this lot. First of all, that, that. Strip 20 foot strip is. Is part of the lot. Within that 20 feet, there has to be a underground power. Water and driveway. And there is quite a cross slope on the. On the lower part of that. That we. Think will be an issue in terms of. Creating a. Recently level of drive into the lot. Without encroaching on the neighbors. Either side. The primary concern, though, with this. This. Development of this lot is the. Wetlands. And the drainage, the stormwater drainage that. Flows onto this lot. Good portion of the lot is wetlands. There would have to be an expert brought in to actually look at that and. Delineate and. Determine the limits of it, but. From the, from the obvious cat tails that we see and so forth. It appears that a good portion is wetland. That wetland functions as a mitigation factor for our stormwater. Coming down behind all of the homes above. There is a main drainage way. That crosses the lot. There's also a drainage way from Point Ridge road, which you can see on the aerial photo that we're looking at. That has cat tails in it. And that veers into the 20 feet near the bottom of the. The. 20 foot section there. There's another drainage that comes off of the hill. So there's a confluence of three drainages on this lot. As well as the wetlands. So we would simply like to. Request as we said in our letter that the board defer the. The waiver on this curb cut until these other issues are resolved. A site plan is developed to scale. Showing the limits of the wetland. The drainages. How the drive is actually going to be constructed. Without filling in wetlands. Which we know is not permitted. And how. The owner intends to stay within the 20 feet that he has. Without approaching on the neighbors to do cuts and fills and to make this. This drive work. We have no problem with the decision on will go. Whatever the board says on the curb cut itself. But that's sort of a minor point. Compared to the environmental concerns we have. In developing the law. I think that's. I think the letter kind of speaks for itself in that regard. So. Found your little telling. One member of the board but I have to tell you that. That really has nothing to do with what the board is considering tonight. What is not considered whether the law should be developed and not be developed. Or is not considering you know. Complications and drainage. Really is only saying this is between drives. And. Frankly I. From my perspective it kind of beats the standards laid out here. That the board must find. I mean it. Low Vine Road. Without even looking at that's the next standard which is. Not physically feasible. Unless only has another alternative of how to do this. I don't see how it's physically feasible to access a lot without using this drive. Just my opinion. Board is not made a decision by any means but. Just responding to those issues just put these respective. You have not asked for party status so. Right now you're just speaking as a. Friend. Well I'll explain that we don't have any intent. Of. Appealing. Of the decision of the board regarding the current cut. Okay. So that's why. You know. We don't need to. Request party status. Thank you. I may ask. The authority of the. Architectural control committee within the association. Do the final. Development have to come to you for approval and do you have the authority. As the ACC to with all that approval. We believe we do. Okay. And then. Mr. Baker what is the width of the proposed drive way. Well your standard residential drive way is around 12 feet in width. I mean it could be a tad. Could possibly be 10 feet but. 10 to 12 feet is typical. For you know. A residential drive that services one. Home. And is there an existing culvert across the road right there. There is. There is a cross culvert. On Point Ridge Road. So that's something that's like. Those like there's a catch basin there. No it's just an open culvert. All the all the flow from. One side of the other road crosses right there. And joins the other side. And it all goes down onto this lot. I think a site visit would really help but. Again if you're narrow focus is just. I have to tell you I think our focus is narrow. I think the select board probably has more prerogative. In granting a curb cut or not granted curb cut or any conditions attached to it. But we're really dealing with distance between curb cuts. That's the only thing we're dealing with tonight. And frankly. Again you pointed out or somebody just pointed out that. Joe Mr. Baker did that basically. We're dealing with it. A plan to present. Planetary development which is designed to have compact. Development. And so. It's expected that. Driveways. Most most of us don't have a hundred feet five feet. In front of you. So. I'm not sure that hundred feet five feet is appropriate standard for a road this world. That's sort of state standard. Is it correct to say that you're recommending to the select board that this curb cut. If. Be granted the waiver if that's your decision. We have made a decision. If that's your decision it would be a recommendation to. It would be it would be it would be approving. The curb cut. Our action would be to approve or not prove. Make. The way. Yeah. The way. The standard. Yeah. It does not improve a perfect. This board doesn't have. We don't. That's right. And that'd be I guess I don't say a concern. You know for the applicant that. Don't misjudge. This action. As meaning it you know. Yeah. The type of. I think for hundreds. You know the select board would have to follow. It's just a very narrow focus that we're dealing with tonight. You know there are a lot of significant issues that the ACC has brought up. You know it's I think are going to be dealt with it's just not within. Our control is this board. To do. Really only thing we have is we have the ability to wave space to wave that space. Correct. And. That's what we're hearing. Is there any argument why we should. Not wave that space. Based on these criteria. I have just a point of clarification please. Kissing down. Can you state your name please. Make provost. Thank you. So. Make. Last name again. Pro ghost. Thank you. Sorry. And the cameras are tough to pick up. I'm laboring there again instead of being affected by. Masks. So if if I'm looking. At. The. Property. For this lot. The way the lot is designed. It goes between Mr. Liger stats. Driveway. And. Mr. Dricers. And in between there. Is a. The culvert that Bernie was talking about that will run parallel. With the driveway that he intends so do I understand correctly that. Anywhere between Marty's property line. And. The culvert. Mr. Baker could put in his driveway. Is that is that how I'm understanding the curve cut. He could not could he or could he not consider that culvert. To be part of his allotted space. To put the curve to put the driveway. It's not his property. Depends where the property is very. Very. I guess. You're asking a legal question. You're asking a legal question. Does. Does the association or someone have. Permission from the property owner to have that covered there. Now the culvert we're talking about is a cross culvert within the right of way the town right of way the road. Okay. Nothing to do with the driveway. In all honesty I don't think. Again. We're speculating on where a call word is. I don't think we could even answer that question for me. There was a survey. You could point to it. The definitive line. We can't answer that question. The applicant will have to ask answer that question. With any supplicant supplicant application. Application to the select board. This board cannot answer that question. We're just we're just asked to digress spacing. 155 feet. It'd be less than 155 feet for the next drive. That's really what we're being asked. There is there is an initial consideration. That can be approved under the same bylaw and that has to do with shared driveways. But that would require cooperation between property owners. But shared driveways are a reasonable solution to a problem like this or a possible solution problem like this. That's not within the purview of the DRB to insist on a shared driveway. If these were a new subdivision of some sort. We can insist on these driveways being shared. But these are two separate property owners. That's the next part of the same section. Now is there also a manhole on the Leggerstit property? It's in the right away. It's in the right away? Okay. We're not right away with his property. Is that a sewer manhole? Yes. I believe so. That's what I saw. I was looking at Google Maps and I saw this manhole. Is there anything, Tom, as far as spacing between the manhole and the driveway or nothing would affect the operational manhole? Nothing in our bylaws. So again, our bylaws are pretty straightforward. We're looking at simply spacing of driveways. Is there any additional testimony from neighbors or vastspeakers? All the brosses. It's going to be Lewis or Acer. So if you look at this aerial view, the driveway. Pull it up so they can see what you're talking about. You guys don't have that? They do, but so you can point out and describe it. The distance between this orange driveway and the Leggerstit driveway is less than 8 feet, so I can tell if at 155 feet, your ride sounds like a lot, but what would be too little spacing between this driveway and another driveway? I mean, 8 feet is not very much. Right? No. I would say mine's 5 or 6 feet. From your neighbor's driveway? Right. I'm at the end of the cul-de-sac there. It's not unusual. The very top. You guys are going to have driveways that close? Yeah. Right? It's not unusual. Anywhere in this town to have driveways that close? As long as there's room for the snow. Snow banks. That's all the best for them. Yeah. Questions by board members? Tom, do you have any useful comments? No, thank you. There's a lot of cars being stored down there. Sorry? I'm sorry. I'm sorry. I'm sorry. I'm sorry. I'm sorry. I'm sorry. I'm sorry. It's my comment. Mr. Baker, do you have any additional comments you want to make? I would just. Suggest that. The town of Berlin has been taxing me as though this was a viable house lot. For the last. 25 years or so. So I've been kind of operating under that. Delusion. Just a testimony of everyone's offer. Hearing none. I would take a motion to close the hearing portion of this application. So moved. Second. Motion has been made. Seconded by two or first. All those in favor of that motion, please sit by by saying aye. Aye. Aye. No one's opposed. So this hearing is closed. We thank you all for attending. Thank you. The board will probably do a delivery session now. So we're probably going to ask her to leave. In fact, I wouldn't take a motion to go to the board for the session. All right. So moved. All right. Seconded by two or first. Thank you. All those in favor of that motion, please sit by by saying aye. Aye. Thank you. Good night.


Hi, my name is August Siminelli and I'm a technical marketing manager at Red Hat. And today I want to tell you about the new AWS controllers for Kubernetes feature for OpenShift and AWS. This is a new component of OpenShift which helps customers who are running clusters in AWS by allowing them to describe AWS resources from directly within their Kubernetes environments. So let's go ahead and look at a standard developer environment. We've got a developer working with an OpenShift deployment running in Amazon. The developer likes to code against the Kubernetes API to deploy an application. There may be services, deployments, anything out there to allow a customer to consume it. But what about when the developer wants to extend that into the Amazon space? They want to bring in AWS resources, S3, RDS, EC2, something like that. Then the developer has to use a different form. They can't go through the Kubernetes API and this can create some confusion. But of course there are ways to do it with Amazon. You might use the APIs, cloud formation, or the AWS web console. But the problem is you get into a state where there are multiple methods being used and it takes away from the efficiency of the developer. So what can we do to get around that? Introducing the Amazon controller for Kubernetes or AC. So what exactly is AC? Well, AC stands for AWS controllers for Kubernetes. With AC, you can take advantage of AWS managed services for your Kubernetes applications without needing to define resources outside of the cluster. AC provides a consistent and familiar Kubernetes interface for AWS by installing a custom controller, CRD, and RBAC for each AWS service. This means that instead of using the AWS web console or cloud formation, a developer can use the Kubernetes API to describe all the resources their application requires, including AWS resources. AWS controllers for Kubernetes are a collaborative upstream project with a multi-vendor community. There is extensive documentation and examples available online. And the code for the controllers is generated automatically from the AWS APIs, allowing for rapid and ever-growing support of AWS services. So as you can see, AC can take the place of the need to use those external methods, allowing the controller to directly manage the Amazon resources. This replaces the need for the developer to interact with Amazon and instead allow the Kubernetes API to control the controller, meaning the developer sees a consistent flow through OpenShift straight through to AWS. And here's the really good part. To get an AC controller into an OpenShift cluster and to hand over the AWS service management, you can use the operator lifecycle. What this means is you can use an operator to install each and every AC controller. It makes it super easy. Let's go ahead and take a look at the process to make this happen. First, we need to create an account in IAM for the AC operators. You can create this account in the web console, but I've chosen to do it using the AWS CLI. This account can be any username, as there's nothing in the operator or AWS that checks for a specific name. In this case, I'm using a default service account and will attach all policies to it, but you could create an account for each controller for finer control. We create an access key to allow for programmatic access. We'll need these values for later. Now it's time to attach the AWS policies to that user. This allows the controller to interact with the resources across AWS. Each service controller repository provides a recommended policy ARN for use with the controller. For this example, I'll be setting up an S3 operator and an ECR operator. With our AWS environment now set up, we need to create some assets in OpenShift to prepare for our operators. We create a dedicated project to keep things tidy, and then a config map to provide some environmental configuration. It contains information on how the controller should run, which region in AWS the resource should be created in, and which namespace to watch for requests. This is required beforehand by OLM and does not contain any IAM information. A secret is created containing the access keys for the account. The operator will reference this secret to access AWS. Now it's time to install the operators themselves. This follows the familiar procedure used for any operator. Visit operator hub, find the AWS operator you want, and install. But please do note, at this time the ACQ operators are community support only. When installing, you can choose the channel, the installation mode, the namespace, and the update strategy. For this demo, I'll install and demonstrate the S3 and ECR controllers. We'll speed up the video to show the process in its entirety. And now both operators are installed. So let's take a look at some of the resources created by the operator. We see the controllers running in their pods, one for each service. We see the controller's services, deployments, and replica sets. Each operator also installs a CRD for its AWS service. Diving into the CRD, we can see it offers quite a comprehensive spec, with a lot of options for interacting with the AWS service it represents. If we explain one of those available options, for instance the S3 bucket command, we can start to learn how to use the CRD. So let's go ahead and give this a try. We will now create an S3 bucket and an ECR repository using Kubernetes custom resources. First, let's use the AWS CLI to see what we have. We can see a single S3 bucket. It's our registry created as part of the Rosa install. And we don't have any ECR repositories. And here's a simple CR for an S3 bucket. As you can see, our CR is very simple. It's a great way to start. It creates a bucket with some tags and a specific name. So let's apply the CR and use the AWS CLI to check again. And there it is. We now have got an S3 bucket created entirely from a Kubernetes custom resource via the Kubernetes API. Now, the app controller manages this custom resource and therefore all the underlying AWS resources. So we can use OpenShift to query and manage the AWS resource via the Kubernetes API. Let's do the same for ECR. I've sped up the video slightly to show things in their entirety. You can also create custom resources via the UI. Let's take a look at the OpenShift developer view to see the ACK integration with the UI. Creating a new AWS resource from within OpenShift is pretty easy. The operator installs comprehensive and detailed forms that can be filled out to create the resources. Not only is it easy to use, but it's a great way to learn the options available in each CRD. Here we're going to create another S3 bucket and ECR repository via the GUI. I've sped up the video so you can view the process in its entirety. And of course, all these resources are visible in the AWS console. Here's our S3 buckets from both the UI and CLI create operations. And here are the ECR repositories we created. You can even see the one with the scan on push feature that we asked for in our CR. With AWS controllers for Kubernetes, you can more easily create AWS resources from inside your standard Kubernetes development flow. There are many controllers available today and more on the way. And with easy installation and management with OpenShift's operator lifecycle manager and operator hub, installing and managing controllers is an easy, familiar process. AWS controllers for Kubernetes are available today in the operator hub on your OpenShift environment. Have a look at the many AWS services available and start using them today. Thanks for watching.


ublic. I'm opening this document now. Hopefully it will open. So these are these evaluation criteria as listed here. You can find them in the plan. I believe it's on page 13 or 14. So on your own, you can look at the plan. This just projects will be evaluated by the way in which they do X, Y, Z. Additional criteria can be all of these different things. But these are the factors that. Help with the discussion and help with our own coming to be. I'd be glad to send these to you, but you can find it in the plan as well. So I'm going to close this out. We also have from the plan. There are references to something called goals. Now, there are different definitions in management and in organizations as to what a goal actually is, what an objective actually is. But the essence are these are criteria worth considering associated with the different categories. Some might have more than others. These were all taken from the plan. This page, I think, originated from Andy's spreadsheet, where he took the majority of the contents of the evaluation criteria and goals and put them into a spreadsheet. I'll show that to you in a bit. But the underlying factors for any given category are these types of items. Any member can look at them and look at any project as they wish and say, this is what makes sense to me. This doesn't, but I'm just bringing this to your attention to assist. It may just be I like this project a lot, but it can be helpful to actually, you know, kind of go through a step by step process with each project. This is taken from the CPA plan. We had a thorough discussion about two years ago, I think it was when we were contemplating different types of means for members to come up with their initial ratings and two different types of features came up. One was a just a form. Robin, I believe this was you and it might have just been you or it was you and Sarah Eisender that put this together and it just kind of delineated the steps that were suggested or that actually you went through Robin in terms of how to look at the proposals and I can send these to the committee. OK, so we don't have to talk about them thoroughly here, but, you know, clarity of purpose, eligibility, we know most are eligible. Other funds sought, feasibility, timeline, urgency, budget, what are the town committee says and what town funds are applied to this work, etc. That's one method of thinking about things. Another method, which I'll show in a moment here is one that Andy did a lot of work on to put together to have a more mechanized, for lack of a better term, way of looking at the projects. Some people liked using the forum. Some people like using the spreadsheet I'm going to show you. You can use whatever you want and or, you know, just just try to have a consistency with it. So I'm going to display a spreadsheet that's not populated with data, Andy. So this won't have everything that you had previously. And it's not that one, excuse me. I think it was that one. There's two of them. I think it's this one here. You had had a spreadsheet where you had all of the different criteria and projects, and this can be made available. Basically, all the projects were listed that were under community housing, historic preservation, open space and recreation. What's the budget and over on the right hand side are the varying criteria and goals. These are the different goals, primary criteria and additional criteria serves more than one, supports the Amherst sustainability goals, etc. These items across the top and forgive me. I'll let you speak in a moment, Andy, represent the word documents that I and the that I had showed you earlier. But this is actually a means of assigning points to each particular category where they will be summed. And you can consider that as an avenue of doing the rating. I'm just broaching this subject so that you're aware of the different types of thought processes that members have used in the past. Andy, do you want to talk a little bit about this one? Even though it's not populated and complete? Yeah, I can share my screen for that because I have it up there as well. And I actually did help with it. That'd be great. Yeah, I mean, I think the the important thing is just whatever method you use that you're evaluating things consistently. Let's see. Can you guys see the screen? Somebody's in London. Oh, wait, did I move from the wrong screen? Am I sharing? Can you guys see what can you see on my screen? I can see the spread spreadsheet populated. OK, all right. OK, so, yeah, it's the one thing that that. It didn't show up when Sam was walking through. It was just, you know, I've got some some criteria that just that you'd use. So it's not so much a number, you just put your criteria in. And then as as was mentioned, it'll it'll generate a score for you. Again, it's it's a means of doing it consistently. And I find that, you know, when I've done this the last two years, I'll go through the scoring mechanism and then I may I may land on that exact score or may land on something slightly different. But it is that's how it's configured. And I've linked these also to the to our website to get the individual. Prosals as well. This is I'll say I do this in Google Sheets, which is if people aren't familiar with it, it's it's Excel, but it's it's web based by Google. So if anybody wants it, they're welcome to it. I will say it's I won't like support it. All right, not an IT guy, but it's certainly happy to share for folks should be pretty self-explanatory otherwise. Thanks, Andy, for displaying that. I'd like to just add the comment that the one item that came to my mind with your spreadsheet.  How one might weight the numbers of categories that one project has four goals and another has six goals, you know, how one might assign the weights can be determined by the individual. But I kind of adopted a dual method between Andy's spreadsheet for information and I adjusted for the budgets, et cetera, et cetera. I realize this is a lot of information. It's all available to you. But the essence that I'm trying to describe here is that when you look at the proposals, just try to think about them in terms of. You know, what what the plan indicates and what you think of the varying goals and evaluation criteria. Try to compare them being whatever whatever method you use. Look at, you know, how you think qualifies and then come up with a number between one and five. Once we get to that point, then, as a committee, we're going to get together and we're going to have to deliberate about budgets, et cetera, et cetera. We're not going to immediately take any of our ratings and turn them into a vote. We're going to thoroughly go through all the different projects before we vote on anything. We're going to have thorough discussions for all the different parameters, but we don't have high limitations in terms of the next presentation, et cetera. So I wanted to take the time in this meeting to just bring this up. I know the existing six members who are here are already familiar with how they've looked at things and done it. Hopefully, it's not too much information. But any questions from the committee? Any questions from either of you on this? Yes, Michelle. I was just wondering who to direct questions to, you know, breaking the meeting laws, just just general procedural stuff, but I guess also evaluation kind of things. Can I can I talk to you, Sam, or should I just direct it to Sonia? Or yeah, what types of questions? I mean, things that may or may not be some specific to the projects, like just theoreticals or things like that. I would say to CC both myself and Sonia on those. OK, thank you. And it may be you can send it to me and CC Sonia if it's committee processes, if it's financial time indicators, you know, son of Sonia and CC me. The there is information available from the CPI coalition in Massachusetts that has a website. They can be helpful in terms of general information. Open meeting laws is a different category. That's a town. It's a state regulation. There are materials that you should have received at this point in time. I guess I should ask this. Have you and have you met both been sworn in as committee members? Yes. OK, thank you. So there was an open meeting law requirement affiliated with that. Well, I think both Michelle and I have already been on town committees. OK, OK. I think you have to do it for every committee, though. You have to get sworn in each time. But that would be my recommendation that. CC email myself, and or Sean, Sonia, depending on the question. Any other questions or comments? Um, so we, you know, Andy indicated that if anyone has an interest in looking at that, maybe we could share it in time for the next meeting, perhaps. And Robbins, they weren't part of the committee here, but I can see to it that they get me emailed. I see a thumb up. So I think we'll email both of those forms. No need to use them. Just take them for what you will. But as a committee, collectively, we've been put together to discuss. All these projects on behalf of the town and collectively, the decisions tend to get made usually. So that's how we're going to go forward. This has been a long meeting. We have another we have no meeting next week, Thanksgiving weekend holiday, and we will next meet on the 8th of on the 1st of December. One thing that comes to mind for me is if we have additional questions for presenters that have already occurred. I know Dave had a couple of two simple questions. Can you get by this year with less, essentially? And, you know, it can this be phased or delayed? I think we'll ask those of everyone. But if any of you have questions on the the presentations that have already occurred or pending questions that might come up for the next one, please send them to Sonia and myself because they can be put together and we can send these out to the applicants in advance of our deliberations that usually is yes, Tim. Yeah, I just want to have a little different subject, but a quick question and clarification on the reserves. We talked about that earlier in the meeting. And roughly we have five roughly five hundred thousand dollars in reserves. They can be used in two ways. One, it could add to the total request for fiscal twenty four. So if the twenty four requests are a million, we could add five hundred. So we in effect could quote spend or allocate one point five rate. That's number one. Number two is the one I was a little bit unsure of. And that is we could find if we find a project has merit like right now before the end of fiscal twenty three. We could we could recommend use of the reserves for fiscal twenty three if we allocate before June 30th within that five hundred thousand. Is that correct? Or am I right? That's correct. OK, so just putting that in our mind as we think through the projects. OK, thanks. Um, just keep in mind, it still has to go through the same process. It still has to go to the finance committee. It's to go to the council to be voted. I missed that step. Sorry about that, Sonia. I missed the step of going through the finance committee prior to going to the council number of applicants asked about the process. Well, there's a process. Yeah, thank you for bringing that up. And I could have informed them. So we'll send out the two different forms that some have used in the past. Members, just consider all the different proposals. We need to hear all the applicants where there are, I believe, five more that we have yet to hear from. And they weren't the same openness of thought as the others. And then we'll go forward. It's a busy time of year for us. Thanks to everybody for sticking through this long meeting. And again, if you have questions that you come up with in the last two sets of presentations today and on the 10th or ones that you anticipate or the others, please try and email them over the course of the next week to Sonia and myself together. Other than that, unless there's something someone has to say at this point in time, I'm going to go ahead and adjourn the meeting at nine oh four p.m. We will meet next December 1st, where we will have the next set of presentations. Thank you. Night, everybody. Night.


Intranasal inactivated influenza vaccines, IIVs, have shown promise as a protective tool against seasonal influenza, with studies indicating that they can induce mucosal immune response and protect against a broad spectrum of influenza virus strains. This article was authored by Corey Sonno, Akira Ainae, Tadaki Suzuki, and others.


Kevin, we talked about how important each of these games are down the stretch you guys have now won six of seven What do you like about the way you guys play tonight and the way you guys have played during the stretch? We hated how we played In our last home game the first half was terrible We wanted to build on that second half this game So we came out with more energy to start and we kind of we stuck with it throughout the whole game So everybody contributed tonight the fans were incredible as always and glad we got it up You took over in that third quarter with 15 points you have 37 nine and eight on the night What sparked you in that third quarter to take over the ballgame just do was required You know they were switching a mismatch on me So I felt like I needed to score every time down my three-point it was working my teammates kept looking for me So I got to finish the job and I'm glad I did in that third You joked this morning about getting old or you move up higher on the all-time scoring list Passing Jerry West what is accomplishments like this mean to you? Oh Jerry somebody I look up to somebody I spent some time with one of championship together So you know it's it's cool to pass him up You know such a legend in the game, but I got more to do special. Thank you so much Kevin