The reaction of an aromatic heterocycle with a proton is called a protonation. One of articles about this theory is 《Camphane derivatives. VII. Syntheses and structure of 3-methyl-3aβ,7aβ-bornano[3,2-d]oxazolidin-2-one and its derivatives》. Authors are Hamashima, Yoshio; Tori, Kazuo; Takamizawa, Akira.The article about the compound:(1S,3R)-1,2,2-Trimethylcyclopentane-1,3-dicarboxylic acidcas:560-09-8,SMILESS:CC1(C)[C@@H](CC[C@]1(C)C(O)=O)C(O)=O).Product Details of 560-09-8. Through the article, more information about this compound (cas:560-09-8) is conveyed.
cf. CA 62, 4055b. In connection with the elucidation of the structure of I and II, obtained by the reaction of 3α-methylaminocamphor (III) with COCl2, 3-methyl-3aβ,7aβ-(IV) and 3aα,7α-bornano[3,2-d]oxazolidin-2-one (V) and their derivatives were synthesized and studied stereochem. Their N.M.R. spectra were also investigated (tabulated and discussed). Excess COCl2 in C6H6 added dropwise with stirring to a boiling suspension of 10 g. III.HCl in dry C6H6 until dissolution gave 7 g. VI, m. 82° (Et2O-hexane), [α]25D 142° (CHCl3), showing a pos. Cotton effect on optical rotatory dispersion (ORD), 0.36 g. II, m. 193° (MeOH-Et2O), [α]25D 127.7° (CHCl3), showing a pos. Cotton effect on ORD, and 0.3 g. unchanged III.HCl. The resinous oil obtained on concentration redissolved in C6H6, the solution washed with 10% aqueous Na2CO3, dried, and concentrated, the oily residue kept several days (HCl evolved), the resulting solid extracted with Et2O, and the Et2O-soluble fraction washed with dilute aqueous Na2CO3, chromatographed on neutral Al2O3, and eluted with Et2O gave 5 g. I, m. 82° (Et2O-hexane), [α]25D -22° (CHCl3), showing a neg. plain curve on ORD; the product eluted with MeOH and the Et2O-insoluble solid combined and recrystallized from MeOH gave 0.40 g. II. VI (0.2 g.) refluxed 2 hrs. with 5 ml. 25% MeOH-HCl gave 0.092 g. I and 0.046 g. VII, m. 122°. VI(0.5 g.) refluxed 5 hrs. with 3 ml. SOCl2 gave 0.35 g. I, m. 82°. (VII,R=Me); (IX,R=Et); (X,R=Ac); (XI,R=Bz); A suspension of I in 4 ml. 2% HCl heated 30 min. at 80° on a steam bath until CO2 evolution ceased and the resulting solution concentrated to dryness gave 15 mg. III.HCl, m. 238° (decomposition). ClCO2Me (1 mole) added dropwise to 2 moles III in Et2O with stirring and ice cooling and the mixture stirred 1 hr. at room temperature, gave VIII, b1, 130-40°, m. 53-4°. A mixture of 100 mg. I and 200 mg. KOH in 10 ml. MeOH refluxed 10 hrs. gave VIII, b1 135°, m. 50°. I (480 mg.) in 5 ml. MeOH containing 500 mg. Na heated 30 min. at 70° gave 400 mg. VIII, b1, 130-40°. I (1 g.) in 15 ml. 30% MeOH-HCl refluxed 10 hrs. gave 0.6 g. VII, m. 122°. I (1 mole) in C5H5N heated 2 hrs. at 70° with 1.2 moles AgNO3 in MeOH also gave VII, m. 122°. I (1 g.) refluxed with 25% EtOH-HCl and worked up like VII gave 0.9 g. IX, b0.07 145°. Both VII and IX were easily hydrolyzed to III by concentrated HCl. A mixture of 2.44 g. I and 2 g. AgOAc in AcOH refluxed 8 hrs. gave 2.1 g. X, m. 107° (hexane), showing a plain neg. curve on ORD. I (240 g.) mixed with 230 mg. AgOBz and 2 g. BzOH, and the mixture heated 10 hrs. at 150-60° and cooled, and the product isolated by extraction with C6H6 gave 200 mg. XI, m. 153-4°, [α]23D -47.2° (CHCl3). Acid hydrolysis of both X and XI led to III, no other products or intermediates being obtained. I (100 mg.) in 10 ml. MeOH containing 200 mg. KOH hydrogenated over 100 mg. 10% Pd-C at room temperature and atm. pressure with stirring (9 ml. H absorbed during 1 hr.) gave 60 mg. IV, m. 119° (Et2O), [α]28D 108.2° (CHCl3), showing a pos. plain curve on ORD. IV was also obtained in fairly good yield by hydrogenation with Raney Ni in alk. medium. 3α-Aminoborneol (XII) (300 mg.) and 3 ml. 98% HCO2H heated 6 hrs. at 110° gave 150 mg. XIII, m. 143° (EtOH). XII (100 mg.) and 100 mg. HCONH2 heated 10 min. at 120° gave 100 mg. XIII, m. 143°. (XII,R=H); (XIII,R=CHO); (XIV,R=Me); (XVIII,R=Cl); (XIX,R=OH); (XXII,R=OAc); (XXIII,R=OMe); XIII (300 mg.) in tetrahydrofuran (THF) added dropwise to 200 mg. LiAlF4 in THF with ice water cooling and the mixture refluxed and stirred 4 hrs. gave 200 mg. XIV, m. 85-6° (hexane). III (3 g.) in Et2O added to 300 mg. LiAlH4 in Et2O and the mixture stirred 2 hrs. at room temperature gave 1.0 g. XIV, m. 85° (hexane). To a mixture of 500 mg. XIV, 10 ml. C6H6, and 10 ml. 10% aqueous Na2CO3 was added 20% C6H6COCl2 with stirring until the organic layer became clear (the mixture was kept alk. throughout the reaction) gave 510 mg. IV, m. 119° (Et2O), [α]26D 108° (CHCl3), IV (10 mg.) refluxed 6 hrs. with 2 ml. MeOH containing 200 mg. KOH gave 6 mg. XIV, m. 80-2°. XIV (200 mg.) and 2 ml. CS2 in 15 ml. EtOH refluxed until no more H2S was evolved (15 hrs.) (during the reaction addnl. CS2 was added) gave 120 mg. XV, m. 206° (MeOH). A suspension of 120 mg. XV and 500 mg. Raney Ni (WII) in EtOH stirred 3 hrs. at room temperature and kept overnight gave 50 mg. XIV, m. 80-2°. To 100 mg. XV in 1 ml. AcOH was added dropwise 35% H2O2 until no more turbidity occurred and the mixture let stand 2 hrs. at room temperature to give IV, m. 119°. 3α-Aminoisoborneol (200 mg.) and 1 ml. 98% HCO2H refluxed 5 hrs. gave 150 mg. 3α-formamido analog, m. 162° (Me2CO-Et2O), which (480 mg.) reduced with LiAlH4 in Et2O gave 300 mg. 3α-methylaminoisoborneol (XVI), m. 66-7° (Et2O-hexane) (HCl salt m. >310°). II (70 mg.) treated with 2 ml. C5H5N and 1 ml. Ac2O under ice water cooling and the solution kept ∼1 week at room temperature gave 60 mg. XVII, m. 120.5° (Et2O), [α]30D 150.3°, showing a pos. plain curve on ORD. XVII on hydrolysis with NaOH or HCl gave II. II(100 mg.) and 2 ml. SOCl2 refluxed 20 hrs. until gas evolution ceased gave 100 mg. XVIII, m. 132° (Et2O-hexane), [α]28D -21.5° (CHCl3), showing a pos. plain curve on ORD. II (100 mg.) and 500 mg. PCl5 in 2 ml. POCl3 refluxed 20 hrs. gave 80 mg. XVIII, m. 130-1°. XVIII (400 mg.) suspended in 10 ml. 10% HCl heated 15 hrs. at 100° gave quant. XIX, m. 254° (decomposition) (MeOH-Et2O), [α]24D 13.3° (CHCl3), showing a pos. plain curve on ORD. XVIII (260 mg.) in 10 ml. MeOH containing 620 mg. KOH heated 4 hrs. at 75° and kept overnight at room temperature gave 100 mg. camphor-quinone (XX), m. 190-5°, and 100 mg. XIX. XIX (130 mg.) in 3 ml. absolute MeOH containing 200 mg. Na kept 1 week at room temperature gave 40 mg. D-camphoric acid (XXI), m. 187° (Et2O-hexane), [α]25D 46.1° (EtOH), and a small amount XX. XXI (10 mg.) heated 4 hrs. at 140° with 10 mg. ZnCl2 and 500 mg. Ac2O gave 3 mg. camphoric anhydride, m. 220°. XIX (50 mg.) in 10 ml. MeOH containing 50 mg. KOH hydrogenated over 100 mg. Raney Ni at room temperature and atm. pressure with stirring (6 ml. H absorbed, during 1 hr.) gave 37 mg. II, m. 188-90°. Zn (600 mg.) added to 130 mg. XIX in 6 ml. AcOH at 100° with stirring, after 2 hrs. 600 mg. Zn added, and the mixture heated and stirred 2 hrs. gave 20 mg. unchanged XIX, and 45 mg. II, m. 190-2°. XVIII (40 mg.), 60 mg. AgOAc; and 1 ml. C5H5N in 1 ml. AcOH heated 3 hrs. at 100° gave 25 mg. XXII, m. 84-5° (Et2O-hexane), [α]22D 67.2° (CHCl3), showing a pos. plain curve on ORD. To 50 mg. XIX in 5 ml. C5H5N was added 1 ml. Ac2O with cooling and the solution kept 1 week at room temperature to give 50 mg. XXII, m. 84° (Et2O-hexane). Treatment of either XVIII or XIX with excess AgOAc in C5H5N gave XXII. XXII (20 mg.) heated 4 hrs. on a steam bath with 2 ml. 10% HCl gave XIX, m. 254° (decomposition) (Et2O). XIX (50 mg.) and 2 ml. SOCl2 refluxed 20 hrs. gave XVIII, m. 132° (Et2O-hexane). A mixture of 40 mg. XVIII, 60 mg. AgNO3; 2 ml. C5H5N, and 2 ml. MeOH heated 1.5 hrs. on a steam bath until no further precipitation of solid occurred gave XXIII, b0.05 110-20°, m. 76-8° (hexane), showing a small pos. plain curve on ORD. XVIII (20 mg.) in 2 ml. 25% MeOH-HCl heated 5 hrs. gave 12 mg. XXIII, b0.05 115°. XXIII (50 mg.) in MeOH hydrogenated over 100 mg. Raney Ni at room temperature and atm. pressure (1 mol. equivalent H was absorbed) gave XXIV, b0.15 120-30°, m. 48-50°. To 260 mg. XIX in AcOD (prepared from 10 ml. Ac2O and 3 ml. D2O) was added 1 g. Zn at 110° with stirring, after 1.5 hrs. 1.5 g. Zn added, and the mixture heated 4.5 hrs. to give XXV, m. 192-3°. XVIII (100 mg.) in 10 ml. MeOH containing 200 mg. KOH hydrogenated over 100 mg. 10% Pd-C at room temperature and atm. pressure (2 mol. equivalents H absorbed in 15 min.) gave 60 mg. IV, m. 119° (Et2O-hexane), and 13 mg. XIV, m. 84-5°. XVIII (55 mg.) in 10 ml. MeOH containing 100 mg. KOH hydrogenated over 200 mg. Raney Ni at room temperature and atm. pressure (2 mot. equivalents H absorbed in 15 min.) gave 28 mg. V, m. 123° (Et2O), [α]27D -33.3° (CHCl3), showing a neg. plain curve on ORD. The N.M.R. spectral evidence confirmed the assignment of the configurations of most of the compounds prepared Pertinent ir data were given and the N.M.R. spectra of IV and V recorded.
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Reference:
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