1 INTRODUCTION
Optically active BINOL and its derivatives are the most prominent C₂-symmetric, axial-chiral ligands，they are well known to apply in asymmetric catalysis and chiral recognition^[1-4]. This is because: BINOL and its derivatives have a chair backbone which can be modified. Substitution of BINOL may affect not only the steric environment around the coordinated metal center but also the electronic properties of the oxygen atoms, which are common constituents of the Lewis acidic metal complexes ^[5-6]. BINOL itself, however, does not always give satisfactory results in asymmetric catalysis, and there has been an ongoing interest in modified BINOL ligands^[7-8] since people's discovery.
    This paper firstly synthesized BINOL-3,3'-dicarboxylic acid (1) under microwave irradiation with iron(III) chloride hexahydrate as catalyst, then a new BINOL derivative 3,3'-diethoxycarbonyl-2,2'- diethoxy-1,1'- binaphthyl (2) was synthesized by substitution reaction.The synthetic routes were outlined in Scheme 1. And its structure was characterized through IR, ¹H NMR, ¹³C NMR and X-ray diffraction, and emphatically analyses its X-ray date.

2. EXPERIMENT
2.1 Materials and general methods
Commercial reagents were used without further purification unless otherwise noted. The melting points were determined using a digital melting point apparatus. IR spectrawere recorded on a Nicolet AVATAR-37ODTGS Spectrophotometer in the region 4000-400 cm^-1 KBr discs. ¹H NMR and ¹³C NMR spectra were recorded on a Bruker Avance-400 superconduct nuclear magnetic resonance instrument, in which chemical shift values are reported in ppm (d) relative to TMS as internal standard. X-ray date was recorded on Rigaku Saturn X ray diffractometer at room temperature.
2.2 Syntheses of 1                        
The BINOL-3, 3'-dicarboxylic acid was synthsized according to reported mothed ^[9]. Iron(III) chloride hexahydrate (20.3g, 56mmol) and 3- hydroxy-2- naphthoic acid fully mixed grind, the mixture was transferred to 100mL beaker, put into a commercial microwave oven Galanz WD800G, set P=20%, t=30s, took out the breaker and stired fully, then put into microwave oven, repeatedly ,till the time of reaction arrived to 740s. The solid was washed by 100mL mixed solution of 36%HCl and H₂O (v/v=1/1), and was collected by vacuum filtration, then purified by column chromatography using ethyl acetate: petroleum ether (3:1, v/v) as the eluent. The main peak was concentrated to afford BINOL-3, 3'-dicarboxylic acid (7.0 g, 18.7mmol) as a yellow solid. Yield: 91%; Mp 295-297^oC (Lit.^[10]Mp>290^oC); ¹H NMR ((CD₃)₂CO, 400 MHz): d 7. 14-7. 17 (m ,2H ,Ar-H) ,7. 39-7. 42(m ,4H ,Ar-H) ,8. 09-8. 11(m ,2H ,Ar-H) ,8. 84( s ,2H ,Ar-H); IR ( KBr) 3059( s ,n_O-H) ,1661( s ,n_{C =O}) ,1499,1455 , 1 272, 1 228 , 1 150 , 1 072 , 886 , 796 , 736cm^{- 1} .
2.3 Syntheses of 2      
At room temperature, compound 1 (0.37g, 1mmol) and NaH(52% dispersion in mineral oil; 0.12g, 2.62 mmol) was added in 5mLDMF, then the mixture was allowed to warm to 50^oC, and stirring for 1.5 h.. After that 1.5mL CH₃CH₂Br was slowly added. Every hour NaH 80mg (1.78mmol) was added in mixture. Tracking the reaction by TLC, until compound 1 reacted completely. Then 10mL H₂O was added to the mixture, extracted with ethyl acetate (3×50mL). The combined organic layers were dried over MgSO₄ and the solvent was removed under reduced pressure. The solid residue was dissolved in ethyl acetate and purified by column chromatography to afford the compound 2 (0.37g, 77%) as a white solid; Mp:104^oC. IR (KBr):2978, 2932, 2898,1725, 1622,1587,1447,1385, 1364, 1339, 1296, 1271, 1227, 1145, 1108, 1070, 1033, 907, 795, 754, 711cm^-1; ¹H NMR(CDCl₃ , 500MHz) d: 0.78-0.81 (t ,3H ,COOCH₂CH₃) ,1.42-1.45 (t, 3H, OCH₂CH₃), 3.47-3.53 (m, 2H, OCH₂CH₃), 3.87-3.93 (m, 2H, OCH₂CH₃), 4.43-4.47 (q, 4H, COOCH₂CH₃ ), 7.13-7.15 (d ,2H ,Ar-H) ,7. 30～7.33(m ,2H ,Ar-H) , 7.41-7,44 (m ,2H ,Ar-H), 7. 95-7. 96(d , 2H ,Ar-H) , 8. 48 ( s , 2H , Ar-H); 13C NMR (CDCl₃,125 MHz) d: 14.3, 15.3, 61.3, 70.3, 77.0, 125.3, 125.7, 125.9, 126.5, 128.2, 129.0, 129.4, 132.7, 135.6,153.7, 166.8.
2.4 X-ray crystallography                           
Crystals of compounds 2 were grown by liquid–liquid diffusion. Mixed solvent of DMSO:H₂O=1:1(v/v)

Table 1. Crystal data and structure refinement for 2

Table2 Selected bond and distance (Å) and angles (°) of 2

3 RESULTS AND DISCUSSION
3.1 Syntheses and spectral analyses                       
Firstly, we synthesized the compound 1 according to reported mothed [9], when setting the power of microwave oven with 20%, the mole ratio n(Iron(III) chloride hexahydrate): n(3-hydroxy-2-naphthoic acid)=1:1.5, the yield was the highest 74% after 740s. The yield had been improved compared with Villemin's report, and the product gives well-resolved ¹HNMR spectra consistent with the report of Jingzhong Yi ^[10].
    In the synthesis of compounds 2, we chose NaH as strong base which can seize the hydrogen at hydroxyl and carboxyl, and it was needed to add intermittently. If the NaH was added much more one time, the DMF would be deduced. If the NaH was added much less, the reaction time would be longer. The compound 2 structure was characterized by IR, ¹H NMR, and ¹³C NMR. The BINOL derivative gives well-resolved ¹HNMR spectra consistent with its structure.
3.2 Crystal structures of compound 2                     
The crystal structure of 2 shows in Figure1, in which the substitutes of naphthalene ring is far, its configuration is R-2, and the dihedral angle of two naphthyl rings is 87.44(9)^o, nearly perpendicular.

Figure 1 the molecular structure of 2

In the crystal cell of 2, every two molecules form a small cuboid channel, four molecules form a bigger cuboid channel, and there are two naphthyl rings are parallel in two adjacent molecules (see Firgure 2 and Firgure 3).

Figure 2 crystal cell of 2 along a axis　

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3,3'-二乙氧甲酰基-2,2'- 二羟基-1,1'-联二萘的合成和单晶结构
李立军^a 李翠哲^a 张大海^b 臧杰超^a
（a河北大学化学与环境科学学院 保定071002 b 邯郸大学化学系 邯郸056005 )
摘要 合成了一种新的3,3'-取代的BINOL衍生物，3,3'-二乙氧甲酰基-2,2'- 二羟基-1,1'′- 联二萘(2)，并且通过IR, ¹H NMR, ¹³C NMR和X-ray单晶衍射等方法对其结构进行了表征
关键词 3,3'-二乙氧甲酰基-2,2'- 二羟基-1,1'- 联二萘；合成；单晶结构