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The Optical Rotation of Liquids Its Variation with Wave Length Temperature, Solvent and Concentration

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The Optical Rotation of Liquids Its Variation with Wave Length Temperature, Solvent and Concentration U. S. DEPARTMENT OF COMMERCE BUREAU OF STANDARDS THE OPTICAL ROTATION OF LIQUIDS ITS VARIATION WITH WAVE LENGTH TEMPERATURE, SOLVENT AND CONCENTRATION By T. MARTIN LOWRY MISCELLANEOUS PUBLICATION No. 118 U. S. DEPARTMENT OF COMMERCE R. P. LAMONT, Secretary BUREAU OF STANDARDS GEORGE K. BURGESS, Director Miscellaneous Publication No. 118 THE OPTICAL ROTATION OF LIQUIDS ITS VARIATION WITH WAVE LENGTH TEMPERATURE, SOLVENT AND CONCENTRATION BY T. MARTIN LOWRY MARCH 25, 1932 UNITED STATES GOVERNMENT PRINTING OFFICE WASHINGTON : 1932 For sale by the superintendent of Documents, Washington, d. c. PREFACE The compilation of the available data on this topic, as presented in the following pages, was made in conjunction with work undertaken for the International Critical Tables and covers, with the exceptions noted below, the literature preceding January 1, 1923. No attempt has been made to include fragmentary data. Data for the sodium D-line at ordinary temperatures and in the common solvents will be found in International Critical Tables. 1 The common sugars have also been omitted from the present compilation, since they have been covered in the saccharimetry section of International Critical Tables. 2 i Int. Crit. Tables, 7, pp. 355-489. McGraw-Hill Book Co., New York; 1931. » Int. Crit. Tables, 2, pp. 334-355. McGraw-Hill Book Co., New York; 1927. CONTENTS Page Preface n L Arrangement 1 II. Symbols and abbreviations 2 III. Class I. Organic substances in which the asymmetric carbon atom does not form part of a ring 2 IB. The molecule contains one carbon atom attached to four different atoms or groups 2 IBi. The asymmetric carbon atom is attached to two other carbon atoms 3 1. Amines 3 2. Monohydroxy alcohols, their ethers and esters 4 3. Amino acids 30 IB2. The molecule contains two asymmetric carbon atoms which are attached each to two other carbon atoms 34 4. Tartaric acid and its esters 34 IQ. The molecule contains one asymmetric carbon atom attached to three other carbon atoms 48 5. Citronellal derivatives 48 6. Amylacetone derivatives 48 IV. Class II. Organic substances, at least one asymmetric carbon atom of which forms part of a ring 49 IIB. The molecule contains asymmetric carbon atoms attached to two other carbon atoms 49 7. Tetrahydronaphthol and derivatives 49 8. Amines 50 IIC. The molecule contains asymmetric carbon atoms attached each to three other carbon atoms 54 9. Methylcyclohexane derivatives 54 10. Dimethyltetrahydroquinoline and derivatives.. 55 11. Myrtenol estersl 56 12. Menthone 56 IIC B. The molecule contains two or more asymmetric atoms at- tached respectively to two and three other carbon atoms 57 13. Menthol, isopulegol and derivatives 57 IID C. The molecule contains two or more asymmetric atoms at- tached respectively to three and four other carbon atoms 66 14. Camphoric and campholytic acids and deriva- tives 66 15. Limonene 68 16. Camphor and derivatives 69 17. Camphorcarboxylic acid and derivatives 76 18. Borneol and related compounds 79 19. Fenchyl alcohol derivatives 81 20. Teresantalic and isoteresantalic acids 82 V. Class III. Compounds containing no asymmetric carbon atom, or containing an asymmetric or dissymmetric atom of some other element 83 (a) Compounds containing asymmetric atoms of S, P, etc 83 21. Methylethylphenacvlthetine deriva- tives 83 22. Bromocamphor- and camphor-sulpho- nates 83 in IV CONTENTS V. Class III—Continued. Page (6) Compounds containing dissymmetric metallic atoms, Co, Cr, Rh, Ir, Pt, etc 84 23. Cobalt complexes 84 24. Chromium complexes 86 25. Rhodium complexes 87 26. Iridium complexes 88 27. Platinum complexes 88 28. Molybdenyl and tungstyl derivatives of malic and tartaric acids 88 VI. Class IV. Substances of unknown, doubtful or complex structure.. 92 29. Alkaloids and derivatives 92 VII. Class V. Influence of salts and other substances on rotatory power. 94 VIII. Literature references 101 IX. Index 105 THE OPTICAL ROTATION OF LIQUIDS, ITS VARIATION WITH WAVE LENGTH, TEMPERATURE, SOLVENT, AND CONCENTRATION 1 By T. Martin Lowry I. ARRANGEMENT Arrangement is by classes denned as follows: CARBON COMPOUNDS 2 I. None of the asymmetric carbon atoms forms part of a ring. II. At least one asymmetric carbon atom forms part of a ring. III. The compound contains no asymmetric carbon atom or con- tains at least one asymmetric or dissymmetric atom other than carbon. IV. Substances of unknown, doubtful, or complex structure. Classes I to IV are subdivided according to the number and nature of the asymmetric atoms as follows: An The molecule contains n asymmetric atoms which are attached each to only one other carbon atom. B„ The molecule contains n asymmetric atoms which are attached each to two other carbon atoms. Cn The molecule contains n asymmetric atoms which are attached each to three other carbon atoms. D„ The molecule contains n asymmetric atoms which are attached each to four other carbon atoms. For substances which fall within two or more of the above sub- divisions the higher (in the order D, C, B, A) division receives prefer- ence in deciding the arrangement. Within a subdivision the ar- rangement is in accordance with the value of n in the order 1, 2, 3, etc. 1 This section includes data and bibliography to January 1, 1924. 1 Sugars and their derivatives are classed as open chain compounds. In general, derivatives are listed under the parent compound, even when they contain additional asymmetric atoms 1 BUREAU OF STANDARDS II. SYMBOLS AND ABBREVIATIONS t Temperature in degrees centigrade (°C). x Wave length of light expressed in Angstrom units; that is, in tenths of a millimicron (Ko mm) unless otherwise indicated. D A wave length of 5893 A. a{ Observed rotation at the given values for t. Ml Specific rotation at the given values for t. [M]! Molecular rotation at the given values for f( = Mx[a]x/ 100). c Concentration in grams per 100 cm 3 of solution. V Concentration in grams per 100 g of solution (= Wt. per cent). (Values in italics when column heading is "c" or "p.") d d{ = density at the given value for t referred to water at 4°C, unless otherwise indicated. 2 per cent NaOH (etc.) 2 per cent of solution of NaOH in water. 2 per cent NaOH MeOH 2 per cent of solution of NaOH in methyl alcohol. M Moles. N NaOH Normal aqueous solution of NaOH ( = 1 equivalent/liter), s Solvent. SYMBOLS FOR SOLVENTS AND RADICALS A ^ The acid radical under Ph = (C 6 H 5 ) Phenyl. which it is used. pn = (C3H10N2) a, jS-Propylene- Ac = (CH 3 CO) Acetyl. diamine. Bu = (C 4H 9 ) Butyl. Pr = (C 3 H7 ) Propvl. en = (C H 8 N 2 a, 0-Ethylene- Py ^ (C 5 H 5 N) Pyridine, ? ) diamine. tr = (C 3 H 10 N 2 ) a, 7-Diamino- Et = (C 2 H 5 ) Ethyl. propane (trimethylene- Me = (CHS ) Methyl. diamine). III. Class I.—ORGANIC SUBSTANCES IN WHICH THE ASYMMETRIC CARBON ATOM DOES NOT FORM PART OF A RING IB. THE MOLECULE CONTAINS 1 CARBON ATOM ATTACHED TO 4 DIFFERENT ATOMS OR GROUPS CHsCUKO^S, ammonium chloriodomethanesulphonate (176) [•IS i c 5,461 5,781 5,893 HjO L 000 15.8 13.3 12.3 H3 L 674 16.0 13.4 12.4 H 2 3. 402 15.7 13.2 12.2 EtOH L671 19.5 16.8 15.7 Notk.—Throughout this paper, black-face figures in parentheses refer to correspondingly numbered citations in the bibliography, p. 101. 1 OPTICAL ROTATION OF ORGANIC SUBSTANCES 3 to a cv^\/^"^/1"c^TTPT^, atotmt tq o 1X3] Tin?1 JtXE< Ao i iVlivlJi I JXlv^ rAPRr>ML-ArCJDVw/iN AO AlATTAPHirn1 AUhbIJ to1 U Z CARBON ATOMS 1. AMINES Sec-butylamine = Am) and derivatives (171) a ( [ ]x° Sulphonyl =Su 5,893 5,780 «=H 2 *\ 5,461 C4H11N. /-Am 1. 4. 70 -5.00 -5.22 -5.75 CtHnClN 1- Am hydrochloride 3. 40 .88 .96 1. 25 CnHuNO Benzoyl-d-Am 1. 00 30.7 32.2 37.1 CioHuNOjS Benzene-Su-d-Am. 3. 01 2. 40 2. 49 2.49 CuHnNOjS. p-Toluene-Su-d-Am 3.03 .81 .81 .81 CiaHuNOjS Naphthalene-a-Su-/-Am 2.73 -5.40 -5.40 -5. 58 Ci5 Hi 5 NO, benzoyl-l-a-phenylethylamine (174; cf. 131) [-R M? 8 c \ 5,893 5,780 6,461 5,461 CeH 6 3. 004 -40. -41.9 -48.3 -137 C.Hj 2.384 -43.7 -45.7 -52.6 -149 C.H. .795 -52.5 -55.7 -64.2 -182 BUREAU OF STANDARDS CO CO CO lO <x>t~-r (CflOtO o oi oi c*"i os SIC «D <*< <N OO CM tt< lO lemon id >d id id id id o id id id id ctccoi 00 r- >o C X CM lO t^-^cd^n ^occ-;H co co co co n w :i ec rj< r~ t— (Occ « O) io >c o *o i ic *r d,ow^ <;hqo &<ooo <* OO O OlOOf 00 lO OS O OS CO 00 I SB, I "NOO) OOOOt^l CM O NOlrtOl ©S00COt~- im ocsooco ooe^j lO CO t~ OS r-C i-( t- o i-i o osododoo t>t^ 8 "3 a 3 jcyl. >> SB ® « O o X! oiz; P 8 e si oqoo oq%% dodo dodo do OPTICAL ROTATION OF ORGANIC SUBSTANCES 5 r 120 r 120 rnyl-1140 Ethyl carbinols (163; cf. 136) a m L J5,461 MS ["]2 [ \d CUHioO Methyl 13. 87 16. 09 10. 02 8. 73 C 6 H,>0 Ethyl Optically inactive. CeHnO „ Propyl 1. 97 2. 24 2. 01 2. 12 2. o2 — CtHisO Butyl 8. 13 9.
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