Category: 121129-31-5

Richard, A. published an article in 1911, the title of the article was Some Derivatives of Pinacolin.Name: Methyl 2-hydroxy-3,3-dimethylbutanoate And the article contains the following content:

cf. C. A., 4, 2303. Methyl pivalate, obtained by adding 62 g. Me2SO4 to 11.5 g. Na in 150 g. MeOH and 50 g. pivalic acid and boiling 30 min., b. 101-3°, d40 0.891. Yield, 90%. Ethyl ester, prepared by boiling 10 g. acid, 10 g. EtOH and 5 g. concentrate H2SO4, b. 120°, d40 0.875. Yield, 85%. A solution of 110 g. in 400 alc. slowly dropped upon 105 g. Na in large pieces gives 40 g. trimethylethyl alcohol, m. 50°, b100 64°, b. 113-5°; phenylurethan, CMe3CH2OCONHPh, from the alc. and PhNCO, m. 114°; pyruvate, b23 78-80°, pyruvate semicarbazone, CMe3CH2OCOCMe : NNHCONH2, m. 166°. CMe3CH2MgCl in Et2O and dry O2 give Me2CEtOH which, when heated with pyruvic acid, yields Me2C : CHMe. With CO2 the Mg compound forms Me2CEtCO2H. Pinacolyl alcohol CMe3CHMeOH, is best obtained (80% yield) by dissolving pinacolin in 5 pts. Et2O, adding 2 pts. 30% K2CO3 and dropping 0.6 pt. Na in small pieces into the mixture; pyruvate, b17 78-80°; pyruvate semicarbazone, m. 17.5°. CMe3CHMeMgCl gives HOCMe2CHMe2 with O2; and with CO2 dimethylisopropylacetic acid, m. 50°, b15 106°. From CMe3CMe2MgCl and CO2 are obtained Me3CCMe3, CMe3CMe2OH (from the O in the air in the apparatus), and CMe3CMe2CO2H. Trimethylpyruvic acid, protected from the air, crystallizes slowly and m. 125°; in the air it crystallizes rapidly, contains 0.5 H2O and m. 90°; oxime, CMe3C( : NOH)CO2H, scales, m. 85°; azine, [CMe3C(CO2H) : N]2 S-yellow needles, m. 207°; semicarbazone, m. 195° (decompose). Methyl ester, b20 69-70°, b. 160-2°, d40 0.994; ethyl ester, b20 76-7°, 0.965. Methyl ester semicarbazone, m. 125°; oxime, m. 66°, b20 125°. Ethyl ester semicarbazone, m. 115°; oxime, viscous liquid, b20 131-3°, gives a few crystals in ice, m. 22-3°; oxime phenylurethan, CMe3C(CO2Et) : NOCONHPh, needles, m. 123-4°. Ethyl α-amino-ββ,β-trimethylpropionate, from CMe3C(:NOH)CO2Et, Zn dust and alc. HCl, b15 83°, d40 0.952; picrate, m. 134°. Ethyl α-phenylurea-β,β,β-trimethylpropionate, CMe3CH(CO2Et)NHCONHPh, m. 78°. Ethyl pseudobutylhippurate, CMe3CH(NHBz)CO2Et from the above amino compound and BzCl, m. 64°, b15 198-200°. CMe3COCO2H, heated with PhNH2, gives the aldehyde and trimethylethylideneaniline, CMe3CH : NPh, which b20 101-2° has d40 0.941, yields CMe3CHO and PhNH2 when heated on the H2O bath with 20% H2SO4. Trimethylacetaldehyde oxime, b20 65°, m. 41°; azine, m. 79°. EtO2CC(CN)(OH)CMe3, allowed to stand 1 week with concentrate H2SO4, gives ethyl pseudobutyltartronamide, EtO2CC(CONH2)(OH)CMe3, m. 60°, b15 162-4°. Alc. NH3 acting 2 hrs. at 100° on CMe3COCO2Et gives a compound C12O21O2N3, m. 225°, whose constitution, owing to lack of material, could not be determined MeMgI and CMe3COCO2Me, or MeMgBr and CMe3COCO2Et give a compound (a) b18 82-3° (see below) and 75-80% of tetramethyllactic acid, CMe3CMe(OH)CO2H, scales, m. 141-2°, b14 130°. The acid can also be obtained from pinacolin through the nitrile (by the action of HCN) which is saponified in 2 ds. by cold concentrate H2SO4 to the amide, m. 140-1°, b10 170° (partial decompose). This, in turn, on boiling with fuming HCl gives the acid. Methyl ester, from the acid, Me2SO4 and NaOMe, b12 65.5°, d40 1.002. Ethyl ester, from the acid, EtOH and H2SO4, b12 74°, d40 0.975. Chloralide, CMe3CMe CHCl3 obtained by heating the acid with 3 mols. CCl3CHO 2 hrs. at 120°, m. 85°, b14 126-7°. From 33.6 g. Mg, 200 g. MeI and 64 g. CMe3CMe(OH)CO2Me were obtained 12 g. of the compound (a) above and 11 g. trimethylpseudobutylglycol, HOCMe2CMe(OH)CMe2, m. 22°, b16 96-8°. The Et ester gives poorer yields than the Me derivative The compound (a) is tetramethyllactaldehyde, b16 82-4°, d40 0.967, does not react with pyruvic acid at 120-30°; is only slightly oxidized by cold alk. KMnO4 to pivalic acid and CMe3CMe(OH)CO2H. Oxime, m. 65°, b15 126-7°, in Ac2O gives with HCl a little pinacolin and CMe3CMe(OH)CN.HOCMe2CMe(OH)CMe2, heated 6 hrs. with 3 volumes 20% H2SO4 gives (CMe3)2CO (Haller and Bauer, C. A. 4, 2092). Trimethyllactic acid chloralide, m. 63°, b15 130°. When heated, the acid begins to lose water at 190° to form the lactide which at 240° begins to evolve CO, giving CMe3CHO (see above). The residue from the distillation of the aldehyde yields the trimeric compound, (CMe3CHO)3, m. 12°, b18 104-5°, d40 0.979, and trimethyllactic acid dilactide, scales, m. 84°, b13 148°. The trimeric compound is depolymerized by distilling at ordinary pressure with anhydrous FeCl3. The aldehyde and HCN give trimethyllactonitrile, CMe3CHOHCN, b100 100°, d40 0.911; with concentrate H2SO4 at 0° this gives after 1 d. the amide, m. 135°, which, in turn, yields the acid when boiled with fuming HCl. Methyl ester, CMe3CHOHCO2Me, b16 69-70°, d40 1.044. Ethyl ester, b16 79-80°, d40 0.987. The acid and PCl5 and MeOH give a compound CMe3CH(CO2Me)OPO(OMe)2, b23 165-70°, d40 1.437, and, in very small quantities, 2 acids, b22 75-90° and 150-5°, resp. The use of PBr5 instead of PCl5, and of PBr3 or PI3 and the Me or Et esters instead of the acid was no more successful in giving the desired compound CMe3CHXCO2R. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).Name: Methyl 2-hydroxy-3,3-dimethylbutanoate

Methyl 2-hydroxy-3,3-dimethylbutanoate(cas:121129-31-5) belongs to ethers. Oxygen is more electronegative than carbon, thus the alpha hydrogens of ethers are more acidic than those of simple hydrocarbons. They are far less acidic than alpha hydrogens of carbonyl groups (such as in ketones or aldehydes), however. Name: Methyl 2-hydroxy-3,3-dimethylbutanoate

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On October 2, 2019, Tanaka, Keita; Ewing, William R.; Yu, Jin-Quan published an article.SDS of cas: 121129-31-5 The title of the article was Hemilabile Benzyl Ether Enables γ-C(sp3)-H Carbonylation and Olefination of Alcohols. And the article contained the following:

Pd-catalyzed C(sp3)-H activation of alc. typically shows β-selectivity due to the required distance between the chelating atom in the attached directing group and the targeted C-H bonds. Herein the authors report the design of a hemilabile directing group which exploits the chelation of a readily removable benzyl ether moiety to direct γ- or δ-C-H carbonylation and olefination of alcs. The utility of this approach is also demonstrated in the late-stage C-H functionalization of β-estradiol to rapidly prepare desired analogs that required multi-step syntheses with classical methods. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).SDS of cas: 121129-31-5

The Article related to benzyl ether alc carbonylation olefination palladium catalyst, General Organic Chemistry: Synthetic Methods and other aspects.SDS of cas: 121129-31-5

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On July 11, 2009, Robertson, Jeremy; Hall, Michael J.; Green, Stuart P. published an article.Formula: C7H14O3 The title of the article was Stereospecific α-methallylation of hydroxyaldehydes by silatropic ene cyclisation. And the article contained the following:

We describe the thermal rearrangement of aldehydes bearing an α-(allyl- or crotylsilyl)oxy substituent. The transformations are best described mechanistically as intramol. silatropic ene reactions based on stereoselectivity, kinetic and computed transition state data. The overall process constitutes a stereospecific (meth)allylation of α-hydroxyaldehydes, under neutral conditions, in which the hydroxyl protecting group is also the (meth)allylating agent. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).Formula: C7H14O3

The Article related to allylsilyloxy crotylsilyloxy aldehyde stereoselective thermal silatropic ene cyclization methallylation, stereoselective thermal silatropic ene cyclization mol modeling, General Organic Chemistry: Synthetic Methods and other aspects.Formula: C7H14O3

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On December 27, 1989, Kaku, Koichiro; Wada, Nobuhide; Sugiyama, Kazuhiko; Takeuchi, Akira; Toyokawa, Yasufumi; Miyazawa, Takeshige; Yoshida, Ryo published a patent.COA of Formula: C7H14O3 The title of the patent was Azinylalkanoates as herbicides. And the patent contained the following:

The title compounds [I; R = Q1, Q2, alkenyl, dihydronaphthyl, tetrahydronaphthyl, 1-oxo-1,2,3,4-tetrahydronaphthyl, epoxycycloalkyl, (substituted) indanyl; R1 = H, (substituted) alkyl, alkenyl, alkynyl, Ph, amino, cycloalkyl, nitrophenylthioalkyl, halo, (substituted) benzyl; RR1 = atoms to complete a ring; R2, R4 = H, alkyl; R2R4C = (O-containing) ring; R3 = H, halo, (substituted) alkyl, OH, cyano, thienyl, naphthyl, dihydronaphthyl, Q3; R5, R6 = H, alkyl; R7 = Ph, alkyl; R8 = H, halo, NO2, alkyl, alkoxy, alkylsulfonyl, etc.; A = alkyl, alkoxy, alkylthio, halo, haloalkoxy, amino; B = H, alkyl, alkoxy, haloalkoxy; X = O, S; Z = CH, N; m = 0-2], were prepared Thus, a mixture of Me2PhCCH(OH)CO2Et, 4,6-dimethoxy-2-methylsulfonylpyrimidine, and K2CO3 in DMF was stirred 3 h at 100° to give pyrimidinyloxybutyrate II. II at 40 g/are postemergent gave complete control of barnyard grass. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).COA of Formula: C7H14O3

The Article related to azinyloxyalkanoate preparation herbicide, Heterocyclic Compounds (More Than One Hetero Atom): Triazines and other aspects.COA of Formula: C7H14O3

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On February 19, 2014, Nitsch, Dominik; Huber, Stefan M.; Poethig, Alexander; Narayanan, Arjun; Olah, George A.; Prakash, G. K. Surya; Bach, Thorsten published an article.HPLC of Formula: 121129-31-5 The title of the article was Chiral Propargylic Cations as Intermediates in SN1-Type Reactions: Substitution Pattern, Nuclear Magnetic Resonance Studies, and Origin of the Diastereoselectivity. And the article contained the following:

Nine propargylic acetates, bearing a stereogenic center (-C*HXR2) adjacent to the electrophilic carbon atom, were prepared and subjected to SN1-type substitution reactions with various silyl nucleophiles employing bismuth trifluoromethanesulfonate [Bi(OTf)3] as the Lewis acid. The diastereoselectivity of the reactions was high when the alkyl group R2 was tertiary (tert-butyl), irresp. of the substituent X. Products were formed consistently with a diastereomeric ratio larger than 95:5 in favor of the anti-diastereoisomer. If the alkyl substituent R2 was secondary, the diastereoselectivity decreased to 80:20. The reaction was shown to proceed stereoconvergently, and the relative product configuration was elucidated. The reaction outcome is explained by invoking a chiral propargylic cation as an intermediate, which is preferentially attacked by the nucleophile from one of its two diastereotopic faces. D. functional theory (DFT) calculations suggest a preferred conformation in which the group R2 is almost perpendicular to the plane defined by the three substituents at the cationic center, with the nucleophile approaching the electrophilic center opposite to R2. Transition states calculated for the reaction of allyltrimethylsilane with two representative cations support this hypothesis. Tertiary propargylic cations with a stereogenic center (-C*HXR2) in the α position were generated by ionization of the resp. alc. precursors with FSO3H in SO2ClF at -80 °C. NMR (NMR) spectra were obtained for five cations, and the chem. shifts could be unambiguously assigned. The preferred conformation of the cations as extracted from nuclear Overhauser experiments is in line with the preferred conformation responsible for the reaction of the secondary propargylic cations. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).HPLC of Formula: 121129-31-5

The Article related to chiral propargylic cation intermediates, Physical Organic Chemistry: Addition, Elimination, and Substitution Reactions and other aspects.HPLC of Formula: 121129-31-5

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On December 16, 2011, Kurono, Nobuhito; Ohtsuga, Kentaro; Wakabayashi, Masanori; Kondo, Tadahiro; Ooka, Hirohito; Ohkuma, Takeshi published an article.Category: esters-buliding-blocks The title of the article was Kinetic resolution of racemic α-tert-alkyl-α-hydroxy esters by enantiomer-selective carbamoylation. And the article contained the following:

Kinetic resolution of sterically hindered racemic α-tert-alkyl-α-hydroxy esters is performed by enantiomer-selective carbamoylation with the t-Bu-Box-Cu(II) catalyst (Box = bis(oxazoline)). The reaction with 0.5 equiv of n-C3H7NCO is carried out with a substrate-to-catalyst molar ratio of 500-5000 at -20 to 25 °C. The high enantiomer-discrimination ability of the catalyst achieves an excellent stereoselectivity factor (s = kfast/kslow) of 261 in the best case. A catalytic cycle for this reaction is proposed. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).Category: esters-buliding-blocks

The Article related to kinetic resolution enantioselective carbamoylation racemic hydroxy ester, Physical Organic Chemistry: Addition, Elimination, and Substitution Reactions and other aspects.Category: esters-buliding-blocks

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On February 20, 2004, Creary, Xavier; Burtch, Elizabeth A. published an article.COA of Formula: C7H14O3 The title of the article was Remarkably Facile Solvolyses of Triflates via Carbocationic Processes in Dimethyl Sulfoxide. And the article contained the following:

A number of triflates have been shown to undergo clean pseudo-first-order solvolysis reactions in DMSO-d6 to give products derived from carbocationic intermediates. Thus, t-BuCH(OTf)CO-t-Bu (5) and t-BuCH2OTf (9) react readily in DMSO-d6 at 25 °C to give a rearranged oxosulfonium salts, and subsequent alkene products where Me migration to the incipient cationic center occurs. t-BuCH(OTf)CO2CH3 (14) gives analogous rearranged products, and 1-methylcyclopropyl triflate (21) gives a ring-opened allylic oxosulfonium salt. These triflates react primarily via kΔ pathways. 6-Methylbicyclo[3.1.0]hex-6-yl triflate (23), bicyclo[2.2.1]hept-1-yl triflate (24), 1,6-methano[10]annulen-11-yl triflate (25), (CH3)2C(OTf)CO2CH3 (26), and (CH3)2CCN(OTf) (29) all react in DMSO-d6 to give carbocation-derived products. PhCH(OTf)CF3 (33) and substituted analogs also react readily in DMSO-d6, and the Hammett ρ+ value is -3.7. This suggests a “borderline” mechanism where the transition state has substantial charge development. The primary feature of these solvolyses is the high reactivity of all of these triflates in DMSO-d6. Thus, these triflates are all more reactive in DMSO-d6 than in HOAc, and for most, rates are faster than in CF3CH2OH. Triflates 5, 21, 29, and 33 are 108-109 times more reactive in DMSO-d6 than the corresponding mesylates. It is suggested that the decreased need for electrophilic solvation of triflate anion, and the high cation solvating ability of DMSO, are the reasons for the high triflate reactivity in DMSO-d6. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).COA of Formula: C7H14O3

The Article related to facile solvolysis triflate carbocation intermediate dimethyl sulfoxide solvent effect, Physical Organic Chemistry: Addition, Elimination, and Substitution Reactions and other aspects.COA of Formula: C7H14O3

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On June 30, 2000, Bessard, Y.; Crettaz, R. published an article.Recommanded Product: 121129-31-5 The title of the article was Rate Acceleration of Nucleophilic Substitution of 2-Chloro-4,6-dimethoxypyrimidine by Sulfinate Catalysis. And the article contained the following:

The use of sulfinates greatly enhances the rate of substitution in the reaction of 2-chloro-4,6-dimethoxypyrimidine with alkoxy or aryloxy nucleophiles. Pyrimidinyloxy derivatives as intermediates for potent herbicides have been prepared in good yields from the readily available 2-chloro-4,6-dimethoxypyrimidine. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).Recommanded Product: 121129-31-5

The Article related to nucleophilic substitution chlorodimethoxypyrimidine sulfinate catalyst, pyrimidine chlorodimethoxy nucleophilic substitution sulfinate catalyst, Heterocyclic Compounds (More Than One Hetero Atom): Pyrimidines and Quinazolines and other aspects.Recommanded Product: 121129-31-5

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On October 22, 1997, Bessard, Ives; Stucky, Gerhard published a patent.Product Details of 121129-31-5 The title of the patent was Process for the preparation of substituted pyrimidines. And the patent contained the following:

Pyrimidines I [R1 = OCHR4COR5, 2-oxo-3-tetrahydrofuryl, 2-oxo-3-tetrahydropyranyl, (un)substituted Ph, pyridyl; R2, R3 = H, alkyl, alkoxy, (un)substituted NH2; R4 = H, alkyl, aryl, aralkyl, CO2H, acyl, alkoxycarbonyl; R5 = OH, alkoxy, aryloxy, alkyl] were prepared by treating I [R1 = halogen] with HOR1 in presence of a sulfinate in a one- or two-step reaction. Thus, 2-chloro-4,6-dimethoxypyrimidine was treated with Me3CCH(OH)CO2Me and MeSO2Na to give 82.7% I [R1 = OCH(CMe3)CO2Me, R2, R3 = OMe]. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).Product Details of 121129-31-5

The Article related to alkoxypyrimidine preparation, halopyrimidine alkoxylation sulfinate, pyrimidine halo alkoxylation sulfinate, Heterocyclic Compounds (More Than One Hetero Atom): Pyrimidines and Quinazolines and other aspects.Product Details of 121129-31-5

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On July 7, 1993, Kirby, Gordon W.; Nazeer, Muhammad published an article.COA of Formula: C7H14O3 The title of the article was Asymmetric induction in the Diels-Alder reactions of α-hydroxy acylnitroso compounds. And the article contained the following:

The hydroxamic acids RCH(OR’)CONHOH (R = Ph, R’ = H, Me; R = cyclohexyl, R’ = H; R = CMe3, R’ = H), derived from a series of α-hydroxy acids, have been oxidized with periodate to form transient, chiral acyl nitroso compounds RCH(OR’)CONO, which were trapped in situ with cyclopentadiene and cyclohex-1,3-diene to give mixtures of diastereoisomeric, Diels-Alder cycloadducts I (n = 1, 2), resp. Cycloaddition at 0°C occurred with moderate stereoselectivity, e.g., both the mandeloyl nitroso compound with cyclopentadiene and the tert-butylglycoloyl nitroso compound with cyclohexadiene gave ca. 5:1 mixtures of diastereoisomers. Much higher diastereoselectivities were observed at -78°C. The mandeloyl nitroso compound, which can form an intramol. hydroxy and nitroso groups, showed higher stereoselectivities than its O-Me ether. The major cycloadduct II of the (S)-mandeloyl nitroso compound III and cyclohexadiene was degraded to the bicyclic oxazine of known absolute configuration. Formation of II as the major product is consistent with preferential endo addition of the hydrogen bonded III from the face anti to the Ph group. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).COA of Formula: C7H14O3

The Article related to diels alder asym hydroxy acyl nitroso, Heterocyclic Compounds (More Than One Hetero Atom): Oxazines (Including Morpholine) and other aspects.COA of Formula: C7H14O3

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