Alder, Kurt published the artcileSubstituting additions. IX. Substituting addition and diene synthesis with methylenecyclobutane, Safety of 1-Methylcyclobutan-1-ol, the publication is Chemische Berichte (1952), 556-65, database is CAplus.
cf. C.A. 44, 2927i. The substituting addition of maleic anhydride (I) to methylenecyclobutane (II), which is similar to the addition of I to methylenecyclohexane and -pentane, is studied. Heating an intimate mixture of 400 g. pentaerythrityl tetrabromide and 410 g. Zn dust in 600 cc. H2O slowly to 85° with stirring and adding over a period of 2 hrs. 300 cc. MeOH in small portions give 70-85% II, b. 41-2°. Heating 25 cc. II and 50 g. I in 50 cc. dry C6H6 in a bomb tube 30 hrs. at 190-5°, washing the reaction product with Me2CO into a beaker, and allowing the solvent to evaporate cause the crystallization of 35% adduct (III), consisting of 1 mol. II and 2 mols. I, m. 170-1°, which, on standing in the open air, changes to a tetracarboxylic acid (IV), m. 165-6°. On catalytic hydrogenation of 1 g. IV in AcOEt with PtO2, the saturated tetracarboxylic acid, m. 193°, is formed. Heating 1.5 g. III and 1.4 g. S 2.5 hrs. at 240-5°, dissolving the reaction products in Na2CO3, oxidizing with KMnO4, destroying the excess KMnO4 with NaHSO3, washing with ether, acidifying, evaporating the filtered solution in vacuo to dryness, and extracting the residue with hot Me2CO give a tetracarboxylic acid (V) of Va as an oil. Oxidation of V with concentrated HNO3 on a water bath and, finally, in a bomb tube at 165° gives trimellitic acid (VI), m. 221°, which, heated above its m.p. and sublimed, gives the anhydride, m. 161°. Distilling the residue of the mother liquor of III in vacuo gives 3 g. of a fraction, b13 155-60°, which, dissolved in Na2CO3, filtered, acidified, and extracted with ether, gives the dicarboxylic acid (VII), of VIIa, an adduct of 1 mol. isoprene and 1 mol. I, m. 155°. When hydrogenated in AcOEt in the presence of PtO2, VII gives 4-methylcyclohexane-1,2-dicarboxylic acid, m. 165°. Heating 1 g. VII with 0.35 g. S 2.5 hrs. at 230-5° and then heating the reaction product with concentrated HNO3, finally 6 hrs. in a bomb tube at 160°, give VI. The formation of VII is the result of a rearrangement of II via CH2.CH2.CH:CMe to CH2:CHCMe:CH2. Heating 20 cc. II and 35 cc. freshly distilled CH2:CHCO2H in 40 cc. dry C6H6 30 hrs. at 200° and fractionally distilling in vacuo the reaction product from 2 runs give 45% distillate (VIII), b13 120-45°. Shaking VIII with ether and dilute KOH, acidifying the alk. solution with HCl, and extracting with ether give 18 g. of an acid mixture which, redistilled, b13 130-8°. It is separated into 7.2 g. crystalline 4-methyl-Δ3-tetrahydrobenzoic acid (IX), m. 100° (anilide, prepared via its Me ester, long needles, m. 154°; hydrazide, long silky nedles, m. 151-2°), and 7.9 g. of an oily adduct (X), CH2.CMe:CH.CH2.CH2.CHCO2H. Hydrogenating IX with PtO2 in AcOEt and treating the Me ester, prepared with CH2N2, with PhNH2 give the anilide of the saturated acid, C14H19ON, long needles, m. 130-1°. Ozonization of 2.5 g. IX in 100 cc. AcOEt with O containing 3-4% O3 and reduction of the reaction product with PtO2 and a few drops MeOH give MeCOCH2CH2CH(CO2H)CH2CO2H, hard crystals, m. 122-3° (semicarbazone, m. 178°). Heating 1 g. IX with 4 cc. concentrated H2SO4 15 min. on a boiling water bath and pouring the mixture on ice give p-MeC6H4CO2H, m. 178°, in good yield. Heating 1.4 g. IX 2.5 hrs. at 230-5° with 0.64 g. S, dissolving the reaction product in Na2CO3, treating it with KMnO4, decolorizing with NaHSO3, and acidifying give p-C6H4(CO2H)2 (di-Me ester, m. 140°). Heating 1.4 g. X 2.5 hrs. at 230-5° with 0.64 g. S gives m-MeC6H4CO2H, m. 110°, which, oxidized with KMnO4, gives m-C6H4(CO2H)2 (di-Me ester m. 68°). Distillation of the residue of the washed ether solution obtained in the working up of VIII gives 10 g. 1-hydroxy-1-methylcyclobutane (XI) acrylate (XII), b13 125°, which (8 g.), refluxed 6 hrs. with concentrated KOH-MeOH, gives XI, b. 117-20° (phenylurethan m. 139°). Ozonization of XII gives HCHO. Acidification of the alk. solution gives 1.5 g. IX. Heating 20 cc. II and 20 cc. AcOH 48 hrs. at 200°, diluting the mixture with H2O, and distilling the washed (dilute Na2CO3, H2O) oil give 9 g. of a mixture, b. 140-200°. Saponification with KOH-MeOH of the fraction, b. 130-60°, gives XI. Refluxing 4 g. of the fraction, b. 170-85°, 4 hrs. with 2 g. I in a little ether, distilling off the ether and unreacted reagents, and dissolving the residue in hot concentrated Na2CO2H give the Na salt of an adduct of I with α-terpinene, as fatty shiny scales. Heating the free acid above its m.p. gives the anhydride, m. 62-3°.
Chemische Berichte published new progress about 20117-47-9. 20117-47-9 belongs to alcohols-buliding-blocks, auxiliary class Aliphatic cyclic hydrocarbon,Alcohol, name is 1-Methylcyclobutan-1-ol, and the molecular formula is C5H10O, Safety of 1-Methylcyclobutan-1-ol.
Referemce:
https://en.wikipedia.org/wiki/Alcohol,
Alcohols – Chemistry LibreTexts