98674-86-3

Usage

InChI:InChI=1/C11H14ClO4P/c1-11(2)7-15-17(13,14)16-10(11)8-5-3-4-6-9(8)12/h3-6,10H,7H2,1-2H3,(H,13,14)/t10-/m1/s1

Synthetic route

(+)-4-(2-chlorophenyl)-dihydro-2-hydroxy-5,5-dimethyl-4H-1,3,2-dioxaphosphorin-2-oxide (98634-28-7) → (S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3)

2-chloro-benzaldehyde (89-98-5) → (S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3)

Conditions	Yield
Multi-step reaction with 4 steps 1: KOH / ethanol / 5 h / 50 - 60 °C 2: POCl3, triethylamine / CH2Cl2 / 3 h / Heating 3: aq. NaOH / 0.25 h / 90 - 95 °C View Scheme
Multi-step reaction with 4 steps 1: D-Prolin / N,N-dimethyl-formamide / 17 h / 25 °C 2: sodium tetrahydroborate / methanol / 20 °C 3: trichlorophosphate / dichloromethane / 4 h / Reflux 4: sodium hydroxide / 1 h / 90 °C View Scheme

1-(2'-chlorophenyl)-2,2-dimethyl-1,3-dihydroxy-propane (98634-39-0) → (S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: POCl3, triethylamine / CH2Cl2 / 3 h / Heating 2: aq. NaOH / 0.25 h / 90 - 95 °C View Scheme

4-(2-chlorophenyl)-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinan 2-oxide (336102-85-3) → (S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: aq. NaOH / 0.25 h / 90 - 95 °C View Scheme

(+)-4-(2-chlorophenyl)-dihydro-2-hydroxy-5,5-dimethyl-4H-1,3,2-dioxaphosphorin-2-oxide (98634-28-7) → (S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) + (R)-(+)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide

Conditions	Yield
With barium(II) acetate In methanol Solvent; Reagent/catalyst; Resolution of racemate;
With C22H24N2(2+)*2CF3O3S(1-) In aq. acetate buffer at 20℃; pH=8.1; Resolution of racemate;

(S)-(-)-3-(2-chlorophenyl)-3-hydroxy-2,2-dimethylpropanal → (S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: sodium tetrahydroborate / methanol / 20 °C 2: trichlorophosphate / dichloromethane / 4 h / Reflux 3: sodium hydroxide / 1 h / 90 °C View Scheme

(R)-(+)-1-(2'-chlorophenyl)-2,2-dimethyl-1,3-propanediol (133164-40-6) → (S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: trichlorophosphate / dichloromethane / 4 h / Reflux 2: sodium hydroxide / 1 h / 90 °C View Scheme

(S)-(-)-2-chloro-4-(2-chlorophenyl)-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one → (S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3)

Conditions	Yield
With sodium hydroxide at 90℃; for 1h;	8.18 g

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → (R)-(+)-1-(2'-chlorophenyl)-2,2-dimethyl-1,3-propanediol (133164-40-6)

Conditions	Yield
With potassium hydroxide In ethylene glycol at 150℃; for 8h;	70%

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(trans-1-propenyl)-1,3-dioxane (133124-13-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 70 percent / potassium hydroxide / ethane-1,2-diol / 8 h / 150 °C 2: 86 percent / 4-toluenesulfonic acid / benzene / 6 h / Heating View Scheme

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → 4-(2-Chloro-phenyl)-2-isopropyl-5,5-dimethyl-[1,3]dioxane (133124-10-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: 70 percent / potassium hydroxide / ethane-1,2-diol / 8 h / 150 °C 2: 85 percent / 4-toluenesulfonic acid / benzene / 6 h / Heating View Scheme

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(trans-1-pentenyl)-1,3-dioxane (133124-18-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: 70 percent / potassium hydroxide / ethane-1,2-diol / 8 h / 150 °C 2: 89 percent / 4-toluenesulfonic acid / benzene / 6 h / Heating View Scheme

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(trans-2-methylcyclopropyl)-1,3-dioxane

Conditions	Yield
Multi-step reaction with 3 steps 1: 70 percent / potassium hydroxide / ethane-1,2-diol / 8 h / 150 °C 2: 86 percent / 4-toluenesulfonic acid / benzene / 6 h / Heating 3: 65 percent / toluene / 3 h / -20 °C View Scheme

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(trans-2-phenylethenyl)-1,3-dioxane (133127-92-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: 70 percent / potassium hydroxide / ethane-1,2-diol / 8 h / 150 °C 2: 89 percent / 4-toluenesulfonic acid / benzene / 6 h / Heating View Scheme

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(trans-2-propylcyclopropyl)-1,3-dioxane

Conditions	Yield
Multi-step reaction with 3 steps 1: 70 percent / potassium hydroxide / ethane-1,2-diol / 8 h / 150 °C 2: 89 percent / 4-toluenesulfonic acid / benzene / 6 h / Heating 3: 88 percent / toluene / 3 h / -20 °C View Scheme

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → (2S,4S)-(-)-4-(2-chlorophenyl)-2-(4-methoxyphenyl)-5,5-dimethyl-1,3-dioxane (133124-08-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 70 percent / potassium hydroxide / ethane-1,2-diol / 8 h / 150 °C 2: 81 percent / 4-toluenesulfonic acid / benzene / 6 h / Heating View Scheme

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(1-methyl-trans-2-phenylethenyl)-1,3-dioxane (133124-15-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 70 percent / potassium hydroxide / ethane-1,2-diol / 8 h / 150 °C 2: 79 percent / 4-toluenesulfonic acid / benzene / 6 h / Heating View Scheme

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(trans-2-phenylcyclopropyl)-1,3-dioxane

Conditions	Yield
Multi-step reaction with 3 steps 1: 70 percent / potassium hydroxide / ethane-1,2-diol / 8 h / 150 °C 2: 89 percent / 4-toluenesulfonic acid / benzene / 6 h / Heating 3: 97 percent / toluene / 3 h / -20 °C View Scheme

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(1-methyl-trans-2-phenylcyclopropyl)-1,3-dioxane

Conditions	Yield
Multi-step reaction with 3 steps 1: 70 percent / potassium hydroxide / ethane-1,2-diol / 8 h / 150 °C 2: 79 percent / 4-toluenesulfonic acid / benzene / 6 h / Heating 3: 76 percent / toluene / 3 h / -20 °C View Scheme

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) → (2S,4S)-(-)-4-(2-chlorophenyl)-5,5 dimethyl-2--1,3-dioxane (133146-58-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: 70 percent / potassium hydroxide / ethane-1,2-diol / 8 h / 150 °C 2: 55 percent / 4-toluenesulfonic acid / benzene / 6 h / Heating View Scheme

(S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (98674-86-3) + ethylamine (75-04-7) → ethylammonium (S)-chlocyphos

Conditions	Yield
In isopropyl alcohol at 30℃;

Upstream product

• 98634-28-7 (+)-4-(2-chlorophenyl)-dihydro-2-hydroxy-5,5-dimethyl-4H-1,3,2-dioxaphosphorin-2-oxide 
• 133164-40-6 (R)-(+)-1-(2'-chlorophenyl)-2,2-dimethyl-1,3-propanediol 
• 336102-85-3 4-(2-chlorophenyl)-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinan 2-oxide 
• 98634-39-0 1-(2'-chlorophenyl)-2,2-dimethyl-1,3-dihydroxy-propane 
• 89-98-5 2-chloro-benzaldehyde 

Downstream Products

• 133164-40-6 (R)-(+)-1-(2'-chlorophenyl)-2,2-dimethyl-1,3-propanediol 
• 133124-13-7 (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(trans-1-propenyl)-1,3-dioxane 
• 133124-10-4 4-(2-Chloro-phenyl)-2-isopropyl-5,5-dimethyl-[1,3]dioxane 
• 133124-18-2 (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(trans-1-pentenyl)-1,3-dioxane 
• 133127-92-1 (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(trans-2-phenylethenyl)-1,3-dioxane 
• 133124-08-0 (2S,4S)-(-)-4-(2-chlorophenyl)-2-(4-methoxyphenyl)-5,5-dimethyl-1,3-dioxane 
• 133124-15-9 (2S,4S)-(-)-4-(2-chlorophenyl)-5,5-dimethyl-2-(1-methyl-trans-2-phenylethenyl)-1,3-dioxane 
• 133146-58-4 (2S,4S)-(-)-4-(2-chlorophenyl)-5,5 dimethyl-2--1,3-dioxane 
• 3899-07-8 (5-methoxy-1,2,3,4-tetrahydronaphthalen-2-yl)propylamine 
• 161873-80-9 (S)-7-methoxy-N-propyl-1,2,3,4-tetrahydronaphthalen-2-amine 

Relevant academic research and scientific papers

Diquats with Robust Chirality: Facile Resolution, Synthesis of Chiral Dyes, and Application as Selectors in Chiral Analysis

Diquats with extremely high racemization barriers with ΔG≠theor of 233 kJ mol?1 at 180 °C are described. Reported configurational robustness is due to a combination of two structural features: the rigid o-xylylene tether connecting the nitrogen atoms and the presence of two substituents in the bay region of the bipyridinium scaffold. The straightforward synthesis of diquats, plus facile resolution and derivatization make them attractive for chiral application studies. This is demonstrated by: 1) synthesis of the first non-racemic diquat dyes with pronounced chiroptical properties, and 2) capability of diquats to interact stereospecifically with chiral molecules. This suggests potential for diquat derivatives to be used as chiral selectors in separation methods.

A method for preparing chiral ring phosphoric acid (by machine translation)

The invention discloses a method for preparing chiral ring of phosphoric acid, the method comprises the following steps: a Isobutyraldehyde, aromatic aldehyde under the condition of chiral catalyst to catalyze the reaction generating chiral 3-aryl-3-hydroxy -2,2-dimethyl-propionaldehyde; chiral b 3-aryl-3-hydroxy -2,2-dimethyl propionic aldehyde reduction to obtain chiral 1-aryl -2,2-dimethyl -1,3-propylene glycol; c in methylene chloride under the conditions of reaction with phosphorus oxychloride to obtain chiral 4-aryl-2-chloro -5,5-dimethyl-2-oxo -1, 3, 2-dioxo-phosphorus heterocycle hexane chloride; in d hydrolysis under alkaline conditions, dyeworks generating chiral ring phosphoric acid. The high optical purity of the target product, the operation is simple, low cost, high yield, less pollution, belonging to the field of organic synthesis. (by machine translation)

Enantiomeric separations of chiral sulfonic and phosphoric acids with barium-doped cyclofructan selectors via an ion interaction mechanism

New cyclofructan-6 (CF6)-based chiral stationary phases (CSPs) bind barium cations. As a result, the barium-complexed CSPs exhibit enantioselectivity toward 16 chiral phosphoric and sulfonic acids in the polar organic mode (e.g., methanol or ethanol mobile phase containing a barium salt additive). Retention is predominantly governed by a strong ionic interaction between the analyte and the complexed barium cation as well as hydrogen bonding with the cyclofructan macrocycle. The log k versus log [X], where [X] = the concentration of the barium counteranion, plots for LARIHC-CF6-P were linear with negative slopes demonstrating typical anion exchange behavior. The nature of the barium counteranion also was investigated (acetate, methanesulfonate, trifluoroacetate, and perchlorate), and the apparent elution strength was found to be acetate > methanesulfonate > trifluoroacetate > perchlorate. A theory based upon a double layer model was proposed wherein kosmotropic anions are selectively adsorbed to the cyclofructan macrocycle and attenuate the effect of the barium cation. van't Hoff studies for two analytes were conducted on the LARIHC-CF6-P for three of the barium salts (acetate, trifluoroacetate, and perchlorate), and the thermodynamic parameters governing retention and enantioselectivity are discussed. Interestingly, for the entropically driven separations, enantiomeric selectivity can increase at higher temperatures, even with decreasing retention.

The Design of Resolving Agents. Chiral Cyclic Phosphoric Acids

A systematic investigation has been started with the twofold purpose of synthesizing efficient resolving agents and of gaining an insight into the factors that contribute to successful resolutions.We report on the synthesis, resolution, and application of a number of chiral cyclic phosphoric acids.Among these acids, 4-(2-chlorophenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (7A) is an efficient resolving agent, being useful for the resolution of amines and amino acids.Acid chloride 20 is a useful reagent for the determination of the ee of chiral amines.The absolute configuration of (-)-7A was determined through an X-ray structure determination of its salt with (-)-(p-hydroxyphenyl)glycine.